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Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors
Authors:Dr. Mohd Nazish  Dr. Mujahuddin M. Siddiqui  Dr. Samir Kumar Sarkar  Dr. Annika Münch  Christina M. Legendre  Dr. Regine Herbst-Irmer  Prof. Dietmar Stalke  Prof. Dr. Herbert W. Roesky
Affiliation:Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077 Göttingen, Germany
Abstract:This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2SiC6H4PPh2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl2 and GaCl3 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 [CuCl2]. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.
Keywords:aluminium  boron  copper  phosphane  silylene
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