The reactions of amides[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(THF)(M=Ca(5),Yb(6))and[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(M=Ca(7),Yb(8))coordinated by a bulky carbazolyl ligand(tBu_(2)CarbAr_(2)=3,6-di-tert-butyl-1,8-bis(3...The reactions of amides[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(THF)(M=Ca(5),Yb(6))and[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(M=Ca(7),Yb(8))coordinated by a bulky carbazolyl ligand(tBu_(2)CarbAr_(2)=3,6-di-tert-butyl-1,8-bis(3,5-di-tert-butylphenyl)-carbazolyl)with PhSiH_(3) allowed for the synthesis of isolable low-coordinate hydrides{[tBu_(2)CarbAr_(2)]MH(THF)}_(2)(M=Ca(11),Yb(12))and{[tBu_(2)CarbAr_(2)]MH(η^(6)-C7H8)}_(2)(M=Ca(11),Yb(12))featuring dimeric structures.Hydrides 11 and 12,as well as amides 7 and 8,proved to be efficient catalysts for PhSiH_(3) addition to pyridines at ambient T.However,the same catalyst at 90℃ catalyzes the opposite reaction:the release of the parent silane and the restoration of the aromatic pyridine system.展开更多
In this paper,we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald[2+2]method,and their reactions with different metal ions afforded three new metalloporphyrin frameworks(MPFs)[Co(...In this paper,we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald[2+2]method,and their reactions with different metal ions afforded three new metalloporphyrin frameworks(MPFs)[Co(tBu-Ph)_(2)(Im-Ph)_(2)Por]·2DMF(1),[Co(F_(3)-Ph)_(2)(Im-Ph)_(2)Por]·1.5DMF(2),and[Fe(Me2N,F4-Ph)_(2)(Im-Ph)_(2)Por]·3DMF(3),which display rich structural diversity.Complexes 1 and 2 are isostructural two-dimensional(2D)grid layers,which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers,as well as the significantly saddled porphyrin macrocycles.Differently,complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles,which contains not only interesting helical channels but also uncommon tetrahedral cages.Gas adsorption studies of three complexes reveal the moderate CO_(2) adsorption capacity.Meanwhile,all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.展开更多
基金The financial support of the Russian Science Foundation is highly acknowledged(Project No.23-73-10148)X-ray diffraction data were collected using the equipment of The Center for Molecular Composition Studies of INEOS RAS(Contract/agreement No.075-00277-24-00).
文摘The reactions of amides[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(THF)(M=Ca(5),Yb(6))and[tBu_(2)CarbAr_(2)]MN(SiMe_(3))_(2)(M=Ca(7),Yb(8))coordinated by a bulky carbazolyl ligand(tBu_(2)CarbAr_(2)=3,6-di-tert-butyl-1,8-bis(3,5-di-tert-butylphenyl)-carbazolyl)with PhSiH_(3) allowed for the synthesis of isolable low-coordinate hydrides{[tBu_(2)CarbAr_(2)]MH(THF)}_(2)(M=Ca(11),Yb(12))and{[tBu_(2)CarbAr_(2)]MH(η^(6)-C7H8)}_(2)(M=Ca(11),Yb(12))featuring dimeric structures.Hydrides 11 and 12,as well as amides 7 and 8,proved to be efficient catalysts for PhSiH_(3) addition to pyridines at ambient T.However,the same catalyst at 90℃ catalyzes the opposite reaction:the release of the parent silane and the restoration of the aromatic pyridine system.
基金the research grant provided by the National Natural Science Foundation of China(21271148,21671158 and 21471124)the Natural Science Foundation of Shaanxi province(2013KJXX-26 and 2014JQ2049).
文摘In this paper,we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald[2+2]method,and their reactions with different metal ions afforded three new metalloporphyrin frameworks(MPFs)[Co(tBu-Ph)_(2)(Im-Ph)_(2)Por]·2DMF(1),[Co(F_(3)-Ph)_(2)(Im-Ph)_(2)Por]·1.5DMF(2),and[Fe(Me2N,F4-Ph)_(2)(Im-Ph)_(2)Por]·3DMF(3),which display rich structural diversity.Complexes 1 and 2 are isostructural two-dimensional(2D)grid layers,which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers,as well as the significantly saddled porphyrin macrocycles.Differently,complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles,which contains not only interesting helical channels but also uncommon tetrahedral cages.Gas adsorption studies of three complexes reveal the moderate CO_(2) adsorption capacity.Meanwhile,all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.
