The reaction of aluminum hydride[(Ar^(BIG)-bian)AlH_(2)]^(−)[Li(THF)_(4)]^(+)(1)(Ar^(BIG)-bian=dianion of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene)with TM(CO)_(6)yields σ-complexes[(Ar^(BIG)-bian)...The reaction of aluminum hydride[(Ar^(BIG)-bian)AlH_(2)]^(−)[Li(THF)_(4)]^(+)(1)(Ar^(BIG)-bian=dianion of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene)with TM(CO)_(6)yields σ-complexes[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)TM(CO)_(4)]^(−)[Li(Solv)_(3)]^(+)(TM=Cr,2;Mo,3;W,4),in which two hydride ligands symmetrically bridge the Al and TM centers.Molybdenum hydride[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)Mo(CO)_(4)Li(THF)_(3)]3b reacts with ammonia through H_(2)elimination to form an amido-bridged derivative[(Ar^(BIG)-bian)Al(μ^(2)^(-)NH_(2))_(2)Mo(CO)_(4)]^(−)[Li(THF)_(4)]^(+)(5).In contrast,the reactions of hydride 1 with Cp_(2)Ni and Cp_(3)Er(Cp=C_(5)H_(5))afford a unique Ni(Ⅱ)(μ^(2)-H)_(2)Al(Ⅲ)complex[(Ar^(BIG)bian)(THF)Al(μ^(2)-H)_(2)NiCp](6)and dihydride[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)Er(Cp)_(2)THF](7),respectively.The latter represents the first crystallographically characterized Er/Al complex.Products 2-7 have been identified via IR and NMR spectroscopy,and their molecular structures were determined via single-crystal X-ray analysis.The electronic structures of 2,3 and 6 were examined via DFT calculations,which revealed direct Al-TM bonding.展开更多
基金supported by the Russian Science Foundation(grant 24-13-00369-the experimental studies,grant 23-13-00139-DFT calculations).
文摘The reaction of aluminum hydride[(Ar^(BIG)-bian)AlH_(2)]^(−)[Li(THF)_(4)]^(+)(1)(Ar^(BIG)-bian=dianion of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene)with TM(CO)_(6)yields σ-complexes[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)TM(CO)_(4)]^(−)[Li(Solv)_(3)]^(+)(TM=Cr,2;Mo,3;W,4),in which two hydride ligands symmetrically bridge the Al and TM centers.Molybdenum hydride[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)Mo(CO)_(4)Li(THF)_(3)]3b reacts with ammonia through H_(2)elimination to form an amido-bridged derivative[(Ar^(BIG)-bian)Al(μ^(2)^(-)NH_(2))_(2)Mo(CO)_(4)]^(−)[Li(THF)_(4)]^(+)(5).In contrast,the reactions of hydride 1 with Cp_(2)Ni and Cp_(3)Er(Cp=C_(5)H_(5))afford a unique Ni(Ⅱ)(μ^(2)-H)_(2)Al(Ⅲ)complex[(Ar^(BIG)bian)(THF)Al(μ^(2)-H)_(2)NiCp](6)and dihydride[(Ar^(BIG)-bian)Al(μ^(2)-H)_(2)Er(Cp)_(2)THF](7),respectively.The latter represents the first crystallographically characterized Er/Al complex.Products 2-7 have been identified via IR and NMR spectroscopy,and their molecular structures were determined via single-crystal X-ray analysis.The electronic structures of 2,3 and 6 were examined via DFT calculations,which revealed direct Al-TM bonding.
