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Updated: Aug 17, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Zirconium complexes having a chiral phosphanylamide in the co-ordination sphere
Michal Wiecko1, Denise Girnt, Marcus Rastätter
1Institut für Chemie, Freie Universität Berlin, Berlin, Germany.
Abstract:
The chiral phosphanylamido ligand, (N(CHMePh)(PPh2))-, has been introduced into co-ordination chemistry. As starting material the oily amines HN(R-*CHMePh)(PPh2)(1a) and HN(S-*CHMePh)(PPh2)(1b) were used. To reconfirm their absolute structure, 1b was oxidized with H2O2 in air to obtain HN(S-*CHMePh)(P(O)Ph2)(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)(PPh2))(3a) and Li(N(S-*CHMePh)(PPh2))(3b) were prepared by deprotonation reaction of 1a,b. Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(eta5-C5H5)2Zr(Cl)(eta2-N(R-*CHMePh)(PPh2))](4a) and [(eta5-C5H5)2Zr(Cl)(eta2-N(S-*CHMePh)(PPh2))](4b). In an alternative approach to give chiral zirconium compounds, the neutral amine 1b was reacted with [(PhCH2)4Zr] to give the enantiomeric pure complex [(PhCH2)3Zr(eta2-N(S-*CHMePh)(PPh2))](5). The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction.
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