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
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.
