Main.Research History
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%center% Highlighted in Chemical & Engineering News (''Model Devised for Polyolefin Catalysts'').
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%center% ''Dalton Transactions'' '''2009''', DOI: 10.1039/b907560g\\
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%center% ''Dalton Transactions'' '''2009''', 8846\\
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Potential single-source molecular precursors [Ba{(μ-ddbfo)'_2_'MR'_x_'}'_2_'] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'_2_'(ddbfoH)'_2_']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'_2_'O'_4_' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'_3_' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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Potential single-source molecular precursors [Ba{(μ-ddbfo)'_2_'MR'_x_'}'_2_'] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'_2_'(ddbfoH)'_2_']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al'_2_' and Ba/Ga'_2_' complexes undergo thermal decomposition to give mixed metal oxides BaM'_2_'O'_4_' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn'_2_' complex decomposes to a mixture of BaCO'_3_' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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The [Mg'''_''2''_''(µ-Cl)'''_3''_''(thf)'''_''6''_'''][TiCl'''_''5''_'''(thf)] compound supported on SiO'''_''2''_''' together with an organometallic cocatalyst is used as a commercial ethylene polymerization catalyst.
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The [Mg'_2_'(µ-Cl)'_3_'(thf)'_6_'][TiCl'_5_'(thf)] compound supported on SiO'_2_' together with an organometallic cocatalyst is used as a commercial ethylene polymerization catalyst.
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Polyolefin catalysts typically are formed from a precursor containing magnesium and titanium chlorides or alkoxides. For the catalyst studied, the precursor is Mg'''_''3'Ti(OR)'''_8''_''X'''_''2''_''' (R = alkyl, X = o-cresol or OCH'''_2''_''_. But the exact structure of the active catalyst is unknown. We instead created an isolable manganese mimic [Mn'''_''3''_Ti(μ'''_''_'''-OCH'''_''2''_'''CH'''_''2''_'''OCH'''_''3''_''')'''_''2''_'''(μ-OCH'''_''2''_'''CH'''_''2''_'''OCH'''_''3''_''')'''_''3''_'''(μ-Cl)Cl'''_''2''_'''(O'''^''i''^'''Pr)'''_''2''_'''] containing a Mn'''_''3''_'''Ti unit and obtained its crystal structure. This model permitted us to visualize the polymerization process. We suggest that the metal atoms of the catalytic site, in which the titanium atom occupies a chiral position, impose a chiral orientation to the growing polymer chain. This effect guides the head-to-tail insertion of olefin units into the chain, which results in a stereoregular polymer.
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Polyolefin catalysts typically are formed from a precursor containing magnesium and titanium chlorides or alkoxides. For the catalyst studied, the precursor is Mg'_3_'Ti(OR)'_8_'X'_2_' (R = alkyl, X = o-cresol or OCH'_2_'CH'_3_'). But the exact structure of the active catalyst is unknown. We instead created an isolable manganese mimic [Mn'_3_'Ti(μ'_3_'-OCH'_2_'CH'_2_'OCH'_3_')'_2_'(μ-OCH'_2_'CH'_2_'OCH'_3_')'_3_'(μ-Cl)Cl'_2_'(O'^i^'Pr)'_2_'] containing a Mn'_3_'Ti unit and obtained its crystal structure. This model permitted us to visualize the polymerization process. We suggest that the metal atoms of the catalytic site, in which the titanium atom occupies a chiral position, impose a chiral orientation to the growing polymer chain. This effect guides the head-to-tail insertion of olefin units into the chain, which results in a stereoregular polymer.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2'ZrCl'''_2''_/MAO/MgCl'''_2''_catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3'µ'''_3''_ -O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'_2_' (MAO = methylaluminoxane) incorporation in the Cp'_2_'ZrCl'_2_'/MAO/MgCl'_2_' catalytic system, which is currently of global industrial use. We show here that the [Al'_3_'(µ'_3_'-O)(Me)'_5_']'^2+^' moiety can be trapped by the tetrapodal [Mg'_3_'Cl'_4_'(thhfo)'_4_'(THF)]'^2-^' macrounit to form a cluster [Al'_3_'Mg'_3_'(µ'_3_'-O)(thffo)'_4_'(Me)'_5_'Cl'_4_'(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'_2_' support surface, which fulfills the requirement of a Al'_3_'(μ'_3_'-O) core.
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Potential single-source molecular precursors [Ba{(μ-ddbfo)'''_''2'MR'''_''x''_'''}'''_''2''_'''] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'''_''2''_''(ddbfoH)'''_''2''_''']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'''_''2'''O'''_''4''_''' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'''_''3''_''' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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Potential single-source molecular precursors [Ba{(μ-ddbfo)'_2_'MR'_x_'}'_2_'] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'_2_'(ddbfoH)'_2_']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'_2_'O'_4_' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'_3_' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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A simple and unique route to access the heterometallic cluster [Mn'''_''4'Ti'''_4''_''(µ-Cl)'''_2''_(µ'_''3''_,η''^''2''^'''-L)'''_''2''_'''(µ,η'''^''2''^'''-L)'''_''10''_'''Cl'''_''6''_'''] ('''1''') with two Mn'''_''2''_'''Ti'''_''2''_''' butterfly core motifs is reported. This method comprises elimination of the Cp ring from Cp'''_''2''_'''TiCl'''_''2''_''' as CpH in the presence of metallic Mn in 2-methoxoethanol (LH) as a proton source. Complex '''1''' belongs to a group of magnetic clusters, which consists of two weakly interacting M'''_''4''_''' subunits.
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A simple and unique route to access the heterometallic cluster [Mn'_4_'Ti'_4_'(µ-Cl)'_2_'(µ'_3_',η'^2^'-L)'_2_'(µ,η'^2^'-L)'_10_'Cl'_6_'] ('''1''') with two Mn'_2_'Ti'_2_' butterfly core motifs is reported. This method comprises elimination of the Cp ring from Cp'_2_'TiCl'_2_' as CpH in the presence of metallic Mn in 2-methoxoethanol (LH) as a proton source. Complex '''1''' belongs to a group of magnetic clusters, which consists of two weakly interacting M'_4_' subunits.
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The reaction of ZnEt'''_''2''_''' with one or two equivalents of aminophenolate ligand N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-cyclohexylamine gives hetero- and homoleptic molecular compounds [(µ,η'''^''2''^-L'''^''2''^)ZnEt]'''_''2''_''' and [Zn(η'''^''2''^''-L'''^''2''^''')'''_''2''_''']. The later is most probably a mixture of diastereoisomers that in solution shows an interesting dynamic behaviour. Both complexes as well as the BnOH derivative of the latter, [(η'''^''2''^'''-L'''^''2''^''')Zn(µ-BnO)]'''_''2''_''', proved excellent initiators for lactide polymerization.
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The reaction of ZnEt'_2_' with one or two equivalents of aminophenolate ligand N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-cyclohexylamine gives hetero- and homoleptic molecular compounds [(µ,η'^2^'-L'^2^')ZnEt]'_2_' and [Zn(η'^2^'-L'^2^')'_2_']. The later is most probably a mixture of diastereoisomers that in solution shows an interesting dynamic behaviour. Both complexes as well as the BnOH derivative of the latter, [(η'^2^'-L'^2^')Zn(µ-BnO)]'_2_', proved excellent initiators for lactide polymerization.
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We describe here a novel, simple, efficient self-assembly method for the in situ generation of [Mn'''_''4'Cl'''_(µ-OCH'_''2''_CH'''_''2'''OMe)'''_''4''_(EtOH)'''_4''_] ('1''') and [Mn'''_''4'Cl)Cl'''_3''_µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(HOCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''3''_''']'''_''2''_''' ('''2''') cubane-type compounds which react readily with calcium species to form cluster [Mn'''_''4''_'''Ca'''_''2''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''8''_'''] ('''3'''), the calcium atoms attached to the Mn'''_''4''_''' unit of '''3''' flatten out the cubane inducing significant conformational changes.
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We describe here a novel, simple, efficient self-assembly method for the in situ generation of [Mn'_4_'Cl'_4_'(µ-OCH'_2_'CH'_2_'OMe)'_4_'(EtOH)'_4_'] ('''1''') and [Mn'_4_'(µ-Cl)Cl'_3_'(µ-OCH'_2_'CH'_2_'OMe)'_4_'(HOCH'_2_'CH'_2_'OMe)'_3_']'_2_' ('''2''') cubane-type compounds which react readily with calcium species to form cluster [Mn'_4_'Ca'_2_'Cl'_4_'(µ-OCH'_2_'CH'_2_'OMe)'_8_'] ('''3'''), the calcium atoms attached to the Mn'_4_' unit of '''3''' flatten out the cubane inducing significant conformational changes.
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The reactions of precursors 4-BrC'''_''6'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6'H'''__''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR ('''8-11''') as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds '''8-11''' were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds '''9''' (R = Me) and '''10''' (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed '''9''' to have a great potential for topochemical 1,4-polymerization.
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The reactions of precursors 4-BrC'_6_'H'_4_'COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'_6_'H'_4_'(C≡C)'_2_'C'_6_'H'_4_'COR ('''8-11''') as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds '''8-11''' were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'_6_'H'_4_'C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds '''9''' (R = Me) and '''10''' (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed '''9''' to have a great potential for topochemical 1,4-polymerization.
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'''Synthesis, structure and thermal decomposition of ''single-source'' precursors for mono- and double oxides with perovskite and spinel-like structure.'''
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'''Synthesis, structure and thermal decomposition of ''single-source'' precursors for mono- and double oxides with perovskite and spinel-like structures.'''
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%center% ''Dalton Transactions'' '''2009''', DOI: 10.1039/b907560g\\
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'''Synthesis, structure and thermal decomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides.'''
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'''Synthesis, structure and thermal decomposition of ''single-source'' precursors for mono- and double oxides with perovskite and spinel-like structure.'''
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Figure)
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Scheme)
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%center% ''Jouranl of Chemical Society, Dalton Transactions'' '''1984''', 2077
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%center% ''Journal of Chemical Society, Dalton Transactions'' '''1984''', 2077
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(µ'''_''3''_'''O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(µ'''_''3''_''' -O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(µ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(µ'''_''3''_'''O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(µ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thhfo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(µ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the [Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)((Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)((Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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The study outlines our initial results that contribute to a better understanding of MAO/MgCl'''_''2''_''' (MAO = methylaluminoxane) incorporation in the Cp'''_''2''_'''ZrCl'''_''2''_'''/MAO/MgCl'''_''2''_''' catalytic system, which is currently of global industrial use. We show here that the[Al'''_''3''_'''(μ'''_''3''_'''-O)(Me)'''_''5''_''']'''^''2+''^''' moiety can be trapped by the tetrapodal [Mg'''_''3''_'''Cl'''_''4''_'''(thffo)'''_''4''_'''(THF)]'''^''2-''^''' macrounit to form a cluster [Al'''_''3''_'''Mg'''_''3''_'''(μ'''_''3''_'''-O)(thffo)'''_''4''_'''(Me)'''_''5''_'''Cl'''_''4''_'''(THF)] (thffo = 2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl'''_''2''_''' support surface, which fulfills the requirement of a Al'''_''3''_'''(μ'''_''3''_'''-O) core.
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%center% ''Inorganic Chemistry'' '''2005''', ''44'', 9131 (Scheme)\\
%center% See also:
%center% ''Inorganic Chemistry'' '''2005''', ''44'', 9131 (Scheme)\\
%center% See also:
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%center% ''Jouranl of Chemical Society, Dalton Transactions'' '''1984''', 2077
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The [Mg'''_''2''_'''(µ-Cl)'''_''3''_'''(thf)'''_''6''_'''][TiCl'''_''5''_'''(thf)] compound supported on SiO'''_''2''_''' together with an organometallic cocatalyst is used as a commercial ethylene polymerization catalyst.
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The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR (8-11) as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds 8-11 were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds 9 (R = Me) and 10 (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization.
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The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR ('''8-11''') as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds '''8-11''' were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds '''9''' (R = Me) and '''10''' (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed '''9''' to have a great potential for topochemical 1,4-polymerization.
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Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis. The group is involved with following projects:
'''Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.'''
'''Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.'''
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'''Synthesis, structure and thermal decomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides.'''
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'''Synthesis of metal complexes and organometallic compounds-precursors for electronic and magnetic materials as well as biomaterials.'''
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'''New catalysts for biodegradable and environment friendly polymers.'''
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'''Chemical models of the active site of nitrogenase and manganese-calcium clusters relevant to photosynthetic dioxygen-evolving centers.'''
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'''Synthesis of organic and organometallic polyynes with potential use as nanoscale electronic devices.'''
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Potential single-source molecular precursors [Ba{(μ-ddbfo)2MRx}2] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'''_''2''_'''(ddbfoH)'''_''2''_''']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'''_''2''_'''O'''_''4''_''' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'''_''3''_''' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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Potential single-source molecular precursors [Ba{(μ-ddbfo)'''_''2''_'''MR'''_''x''_'''}'''_''2''_'''] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'''_''2''_'''(ddbfoH)'''_''2''_''']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'''_''2''_'''O'''_''4''_''' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'''_''3''_''' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR (8-11) as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds 8-11 were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds 9 (R = Me) and 10 (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization
to:
The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR (8-11) as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds 8-11 were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds 9 (R = Me) and 10 (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization.
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The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR ('''8'''-'''11''') as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds '''8'''-'''11''' were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds '''9''' (R = Me) and '''10''' (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization
to:
The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR (8-11) as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds 8-11 were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds 9 (R = Me) and 10 (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization
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The reactions of precursors 4-BrC'''_''6''_'''H'''_''4''_'''COR with TMSC≡CH (Sonogashira coupling) followed by in situ deprotection and subsequent dimerization gave thermally stable dimeric keto-diynes RCOC'''_''6''_'''H'''_''4''_'''(C≡C)'''_''2''_'''C'''_''6''_'''H'''_''4''_'''COR ('''8'''-'''11''') as yellow powders in 25-85 % yields without the necessity of carbonyl group protection/deprotection steps. Compounds '''8'''-'''11''' were also synthesized by an alternative method that utilized α-haloalkynes previously obtained directly from TMS-protected 4-RCOC'''_''6''_'''H'''_''4''_'''C≡CTMS alkynes. The resulting diynes were characterized by spectroscopic methods and in most cases by X-ray crystallography. Careful analysis of the crystal data revealed a surprisingly high degree of chain curvature. Moreover, compounds '''9''' (R = Me) and '''10''' (R = Et) were extremely flat, which greatly facilitates electronic communication throughout the whole molecule. Deeper analysis of the packing motifs showed 9 to have a great potential for topochemical 1,4-polymerization
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Polyolefin catalysts typically are formed from a precursor containing magnesium and titanium chlorides or alkoxides. For the catalyst studied, the precursor is Mg'''_''3''_'''Ti(OR)'''_''8''_'''X'''_''2''_''' (R = alkyl, X = o-cresol or OCH'''_''2''_'''CH'''_''3''_'''). But the exact structure of the active catalyst is unknown. We instead created an isolable manganese mimic [Mn'''_''3''_'''Ti(μ'''_''3''_'''-OCH'''_''2''_'''CH'''_''2''_'''OCH'''_''3''_''')'''_''2''_'''(μ-OCH'''_''2''_'''CH'''_''2''_'''OCH'''_''3''_''')'''_''3''_'''(μ-Cl)Cl'''_''2''_'''(O'''^''i''^'''Pr)'''_''2''_'''] containing a Mn'''_''3''_'''Ti unit and obtained its crystal structure. This model permitted us to visualize the polymerization process. We suggest that the metal atoms of the catalytic site, in which the titanium atom occupies a chiral position, impose a chiral orientation to the growing polymer chain. This effect guides the head-to-tail insertion of olefin units into the chain, which results in a stereoregular polymer.
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We describe here a novel, simple, efficient self-assembly method for the in situ generation of [Mn'''_''4''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(EtOH)'''_''4''_''']('''1''') and [Mn'''_''4''_'''(µ-Cl)Cl'''_''3''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(HOCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''3''_''']'''_''2''_'''('''2''') cubane-type compounds which react readily with calcium species to form cluster [Mn'''_''4''_'''Ca'''_''2''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''8''_''']('''3'''), the calcium atoms attached to the Mn'''_''4''_''' unit of '''3''' flatten out the cubane inducing significant conformational changes.
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We describe here a novel, simple, efficient self-assembly method for the in situ generation of [Mn'''_''4''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(EtOH)'''_''4''_'''] ('''1''') and [Mn'''_''4''_'''(µ-Cl)Cl'''_''3''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(HOCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''3''_''']'''_''2''_''' ('''2''') cubane-type compounds which react readily with calcium species to form cluster [Mn'''_''4''_'''Ca'''_''2''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''8''_'''] ('''3'''), the calcium atoms attached to the Mn'''_''4''_''' unit of '''3''' flatten out the cubane inducing significant conformational changes.
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We describe here a novel, simple, efficient self-assembly method for the in situ generation of [Mn'''_''4''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(EtOH)'''_''4''_''']('''1''') and [Mn'''_''4''_'''(µ-Cl)Cl'''_''3''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''4''_'''(HOCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''3''_''']'''_''2''_'''('''2''') cubane-type compounds which react readily with calcium species to form cluster [Mn'''_''4''_'''Ca'''_''2''_'''Cl'''_''4''_'''(µ-OCH'''_''2''_'''CH'''_''2''_'''OMe)'''_''8''_''']('''3'''), the calcium atoms attached to the Mn'''_''4''_''' unit of '''3''' flatten out the cubane inducing significant conformational changes.
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The reaction of ZnEt'''_''2''_''' with one or two equivalents of aminophenolate ligand N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-cyclohexylamine gives hetero- and homoleptic molecular compounds [(µ,η'''^''2''^'''-L'''^''2''^''')ZnEt]'''_''2''_''' and [Zn(η'''^''2''^'''-L'''^''2''^''')'''_''2''_''']. The later is most probably a mixture of diastereoisomers that in solution shows an interesting dynamic behaviour. Both complexes as well as the BnOH derivative of the latter, [(η'''^''2''^'''-L'''^''2''^''')Zn(µ-BnO)]'''_''2''_''', proved excellent initiators for lactide polymerization.
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A simple and unique route to access the heterometallic cluster [Mn'''_''4''_'''Ti'''_''4''_'''(µ-Cl)'''_''2''_'''(µ'''_''3''_''',η'''^''2''^'''-L)'''_''2''_'''(µ,η'''^''2''^'''-L)'''_''10''_'''Cl'''_''6''_'''] ('''1''') with two Mn'''_''2''_'''Ti'''_''2''_''' butterfly core motifs is reported. This method comprises elimination of the Cp ring from Cp'''_''2''_'''TiCl'''_''2''_''' as CpH in the presence of metallic Mn in 2-methoxoethanol (LH) as a proton source. Complex '''1''' belongs to a group of magnetic clusters, which consists of two weakly interacting M'''_''4''_''' subunits.
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Potential single-source molecular precursors [Ba{(μ-ddbfo)2MRx}2] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)2(ddbfoH)2]·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM2O4 (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO3 and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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Potential single-source molecular precursors [Ba{(μ-ddbfo)2MRx}2] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)'''_''2''_'''(ddbfoH)'''_''2''_''']·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM'''_''2''_'''O'''_''4''_''' (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO'''_''3''_''' and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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Potential single-source molecular precursors [Ba{(μ-ddbfo)2MRx}2] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)2(ddbfoH)2]·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM2O4 (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO3 and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
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-< Potential single-source molecular precursors [Ba{(μ-ddbfo)2MRx}2] (ddbfoH) 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; M/R/x ) Al/Me/2, Al/Et/2, Ga/Me/2, or Zn/Et/1) for mixed metal oxide materials were prepared by the reaction of barium aryloxide [Ba(ddbfo)2(ddbfoH)2]·3ddbfoH with an appropriate organometallic compound in toluene. The precursors were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray structural analysis. The Ba/Al2 and Ba/Ga2 complexes undergo thermal decomposition to give mixed metal oxides BaM2O4 (M = Al, at 1300 °C for both Me and Et derivatives; Ga, at 1430 °C). Instead, the Ba/Zn2 complex decomposes to a mixture of BaCO3 and different metal oxides. The chemical composition and surface morphology of heterobimetallic oxides were analyzed by SEM-EDS and X-ray powder diffraction (XRD) that revealed the formation of highly pure oxide
materials with micrometer particle sizes.
materials with micrometer particle sizes.
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Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis. The group is involved with following projects:
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'''Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis. The group is involved with following projects:'''
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Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis.
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Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis. The group is involved with following projects:
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Research in the Professor Sobota group has been focused around alkoxide and organometallic chemistry, and from this core area branches into catalysis, materials chemistry and organic synthesis.
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Figure)\\
%center% ''Chemical Reviews'' '''2006''', ''106'', 1
%center% ''Chemical Reviews'' '''2006''', ''106'', 1
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Figure)
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%center% ''Chemical Reviews'' '''2006''', ''106'', 1
!! Special equipment
* Glove-box equiped with an inert gas system (MBraun)
* Equipment for cyclic voltammetry measurements
!! Special equipment
* Glove-box equiped with an inert gas system (MBraun)
* Equipment for cyclic voltammetry measurements
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%center% ''Chemical Reviews'' '''2006''', ''106'', 1
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%center% ''Dalton Transactions'' '''2007''', 825 (Scheme)
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%center% ''Dalton Transactions'' '''2007''', 825 (Figure)
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Scheme)\\
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Figure)\\
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%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024\\
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%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024 (Scheme)\\
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%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231\\
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%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231 (Scheme)\\
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%center% ''Dalton Transactions'' '''2009''', 5450 (Scheme)\\
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%center% ''Dalton Transactions'' '''2008''', 6556 (Scheme)\\
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%center% ''Journa; of Molecular Catalysis'' '''2006''', ''257'', 105\\
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%center% ''Journal of Molecular Catalysis'' '''2006''', ''257'', 105\\
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%center% ''Dalton Transactions'' '''2007''', 825
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%center% ''Dalton Transactions'' '''2007''', 825 (Scheme)
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598
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%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598 (Scheme)\\
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%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024
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%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024\\
%center% ''Dalton Transactions'' '''2007''', 2065\\
%center% ''Organometallics'' '''2005''', ''24'', 3987\\
%center% ''Inorganic Chemistry'' '''2005''', ''44'', 9131\\
%center% ''European Journal of Inorganic Chemistry'' '''2005''', 1063
%center% ''Dalton Transactions'' '''2007''', 2065\\
%center% ''Organometallics'' '''2005''', ''24'', 3987\\
%center% ''Inorganic Chemistry'' '''2005''', ''44'', 9131\\
%center% ''European Journal of Inorganic Chemistry'' '''2005''', 1063
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%center% ''Dalton Transactions'' '''2009''', 5450
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%center% ''Dalton Transactions'' '''2009''', 5450\\
%center% ''Dalton Transactions (Perspective)'' '''2008''', 6509
%center% ''Dalton Transactions (Perspective)'' '''2008''', 6509
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%center% ''Macromolecules'' '''2009''', ''42'', 4008
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%center% ''Macromolecules'' '''2009''', ''42'', 4008\\
%center% ''Journa; of Molecular Catalysis'' '''2006''', ''257'', 105\\
%center% ''Inorganic Chemistry'' '''2006''', ''45'', 5302\\
%center% ''Dalton Transactions'' '''2005''', 2047
%center% ''Journa; of Molecular Catalysis'' '''2006''', ''257'', 105\\
%center% ''Inorganic Chemistry'' '''2006''', ''45'', 5302\\
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%center% ''Chemical Reviews'' '''2006''', ''106'', 1
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%center% Attach:EurJOrgChem2008-27-4598.jpg
%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598
%center% ''European Journal of Organic Chemistry'' '''2008''', ''27'', 4598
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%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231
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%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231\\
%center% ''Inorganic Chemistry'' '''2009''', ''48'', 6584\\
%center% ''Inorganic Chemistry'' '''2009''', ''48'', 6584\\
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%center% ''Dalton Transactions'' '''2008''', 6556
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%center% ''Dalton Transactions'' '''2008''', 6556\\
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* Synthesis, structure and thermalvdecomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides
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* Synthesis, structure and thermal decomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides
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%center% ''Inorganic Chemistry'' '''2009''', ''48'', 6584
%center% ''Inorganic Chemistry'' '''2008''', ''47'', 7939
%center% ''Inorganic Chemistry'' '''2008''', ''47'', 7939
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%center% ''Macromolecules'' '''2009''', ''42'', 4008
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%center% ''Dalton Transactions'' '''2007''', 825
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* Synthesis, structure and thermaldecomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides
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* Synthesis, structure and thermalvdecomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides
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* Synthesis, structure and thermaldecomposition of ''single-source'' precursors for perovskite and spinel-like metal oxides
%center% Attach:ChemMater2008-20-4231.jpg
%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231
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%center% ''Chemistry of Materials'' '''2008''', ''20'', 4231
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%center% Attach:DaltonTrans2008-6556.jpg
%center% ''Dalton Transactions'' '''2008''', 6556
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%center% Attach:DaltonTrans2009-5450.jpg
%center% ''Dalton Transactions'' '''2009''', 5450
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%center% Attach:InorgChem2007-46-9024b.jpg
%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024
%center% ''Inorganic Chemistry'' '''2007''', ''46'', 9024
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.\\
%rfloat% Attach:InorgChem2007-46-9024.jpg\\
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”. \\
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%rfloat% Attach:InorgChem2007-46-9024.jpg
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.\\
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.
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* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”. \\
%rfloat% Attach:InorgChem2007-46-9024.jpg \\
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* Glove-box equiped with an inert gas system (MBraun)
* Equipment for cyclic voltammetry measurements
* Equipment for cyclic voltammetry measurements
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HI-TECH SF-51 stopped-flow spectrophotometer
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* HI-TECH SF-51 stopped-flow spectrophotometer
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!! Research areas
* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.
* Synthesis of metal complexes and organometallic compounds-precursors for electronic and magnetic materials as well as biomaterials.
* New catalysts for biodegradable and environment friendly polymers.
* Chemical models of the active site of nitrogenase and manganese-calcium clusters relevant to photosynthetic dioxygen-evolving centers.
* Synthesis of organic and organometallic polyynes with potential use as nanoscale electronic devices.
!! Special equipment
HI-TECH SF-51 stopped-flow spectrophotometer
* Synthesis, structure and reactivity of organometallic and metal complexes – precursors for olefin transformations (polymerization, metathesis, Heck and Suzuki coupling, cyclization, etc.) leading to „fine chemicals” and „chemical specialities”.
* Synthesis of metal complexes and organometallic compounds-precursors for electronic and magnetic materials as well as biomaterials.
* New catalysts for biodegradable and environment friendly polymers.
* Chemical models of the active site of nitrogenase and manganese-calcium clusters relevant to photosynthetic dioxygen-evolving centers.
* Synthesis of organic and organometallic polyynes with potential use as nanoscale electronic devices.
!! Special equipment
HI-TECH SF-51 stopped-flow spectrophotometer
Page last modified on December 17, 2009, at 11:28 AM
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