Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors
Mohd Nazish, Mujahuddin M. Siddiqui, Samir Kumar Sarkar, Annika Münch, Christina M. Legendre, Regine Herbst‐Irmer, Dietmar Stalke, Herbert W. Roesky
Abstract
Abstract This work describes the synthesis and coordination behavior of a new mixed‐donor ligand PhC(N t Bu) 2 SiC 6 H 4 PPh 2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho ‐lithiated diphenylphosphinobenzene (LiC 6 H 4 PPh 2 ) with chlorosilylene (PhC(N t Bu) 2 SiCl). Treatment of 1 with Se and GeCl 2 resulted in Si IV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ‐donor ligand induces dissociation of CuCl and PhBCl 2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl 2 and AlCl 3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl 2 and GaCl 3 forms monodentate complexes 8 and 9 . X‐ray analysis of 4 showed that the copper is in the spiro center of the two five‐membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu + and [CuCl 2 ] − . All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single‐crystal X‐ray diffraction studies.