Zirconium complexes having a chiral phosphanylamide in the co-ordination sphere

摘要

The chiral phosphanylamido ligand,{N(CHMePh)(PPH_2)}~,has been introduced into co-ordination chemistry.As starting material the oily amines HN(R-*CHMePh)(PPH_2)(la)and HN(S-*CHMePh)(PPH_2)(Ib)were used.To reconfirm their absolute structure,Ib was oxidized with H_2O_2 in air to obtain HN(S-*CHMePh)(P(=O)PH_2)(2)as a solid compound.The solid-state structure of 2 was established by single-crystal X-ray diffraction.The lithium salts of both enantiomers Li{N(R-*CHMePh)(PPH_2)}(3a)and Li{N(S-*CHMePh)(PPH_2)}(3b)were prepared by deprotonation reaction of la,b.Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(eta~5C_5H_5)_2Zr(Cl){eta~5N(R-*CHMePh)(PPH_2)}](4a)and [(eta~5C_5H_5)_2Zr(Cl){eta~5N(S-*CHMePh)(PPH_2)}](4b).In an alternative approach to give chiral zirconium compounds,the neutral amine Ib was reacted with [(PhCH_2)_4Zr] to give the enantiomeric pure complex [(PhCH_2)_3Zr{eta~2-N(S-*CHMePh)(PPH_2)}](5).The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction.