Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors
Autor: | Herbert W. Roesky, Regine Herbst-Irmer, Annika Münch, Christina M. Legendre, Mohd Nazish, Mujahuddin M. Siddiqui, Samir Kumar Sarkar, Dietmar Stalke |
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Rok vydání: | 2020 |
Předmět: |
Denticity
chemistry.chemical_element Ionic bonding 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis phosphane chemistry.chemical_compound Chelation P/Si Ligands Full Paper 010405 organic chemistry Ligand aluminium Organic Chemistry Silylene General Chemistry Nuclear magnetic resonance spectroscopy Full Papers Copper 0104 chemical sciences 3. Good health silylene chemistry copper boron Phosphine |
Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) |
ISSN: | 1521-3765 0947-6539 |
DOI: | 10.1002/chem.202003513 |
Popis: | 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. A ligand with different Lewis base donor sites of phosphorus(III) and silicon(II). The ligands are arranged in 1,2‐position at the benzene ring to generate mainly five‐membered ring compounds containing a metal atom. The exceptions of the compounds show clearly that the metal is preferentially coordinated to the silylene atom rather than to the phosphane site of the ligand. |
Databáze: | OpenAIRE |
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