Polyhedron
Polyhedron
4 years ago

Reactions of lithiated diphosphanes R2P-P(SiMe3)Li·nTHF (R=tBu, iPr) with [(PNP)TiCl2]. Two different coordination types of phosphanylphosphido ligand to the metal center

Reactions of lithiated diphosphanes R2P-P(SiMe3)Li·nTHF (R=tBu, iPr) with [(PNP)TiCl2]. Two different coordination types of phosphanylphosphido ligand to the metal center
[(PNP)TiCl2] (PNP=N[2-PiPr2-4-methylphenyl]2) reacts with one equivalent of lithium derivative of diphosphane R2P-P(SiMe3)Li·nTHF (R= tBu, iPr) in toluene and forms the first complex with η 1-coordination [(PNP)Ti(Cl){η 1-P(SiMe3)-PtBu2}] (1) and complex with η 2-coordination [(PNP)Ti(Cl){η 2-P(SiMe3)-PiPr2}] (2) of phosphanylphosphido ligands to the titanium center. The similar reaction with two equivalents of tBu2P-P(SiMe3)Li·nTHF in toluene leads to solid 3 which contains 1 and excess of tBu2P-P(SiMe3)Li in the unit cell. In complex 2 disorder of the phosphanylphosphido ligand was observed. The disorder model shows that the phosphanylphosphido ligand coordinates to the metal center alternately as a bidentate and as a monodentate ligand.

Publisher URL: www.sciencedirect.com/science

DOI: S0277538717305284

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