Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors

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)....

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Bibliographic Details
Published in:Chemistry : a European journal 2021-01, Vol.27 (5), p.1744-1752
Main Authors: Nazish, Mohd, Siddiqui, Mujahuddin M., Kumar Sarkar, Samir, Münch, Annika, Legendre, Christina M., Herbst‐Irmer, Regine, Stalke, Dietmar, Roesky, Herbert W.
Format: Article
Language:English
Subjects:
aluminium
Aluminum chloride
boron
Chemical analysis
Chemical synthesis
Chemistry
Coordination compounds
Copper
Copper chloride
Gallium chloride
Germanium chlorides
Ligands
Magnetic resonance spectroscopy
Mass spectrometry
Mass spectroscopy
NMR
NMR spectroscopy
Nuclear magnetic resonance
Oxidation
phosphane
Phosphine
Phosphines
silylene
Zinc chloride
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Summary: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.
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202003513