An investigation on the chemistry of the R2P=P ligand: reactions of a phosphanylphosphinidene complex of tungsten(VI) with electrophilic reagents - Publication - Bridge of Knowledge

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An investigation on the chemistry of the R2P=P ligand: reactions of a phosphanylphosphinidene complex of tungsten(VI) with electrophilic reagents

Abstract

The nucleophilic properties of the title compound [(2,6-i-Pr2C6H3N)2(Cl)W(η2-t-Bu2PvP)]Li·3DME (1) were investigated in reactions with selected electrophilic reagents such as MeI, M(CO)5THF (M = Cr, Mo, W), AlCl3, and GaCl3. Methylation of 1 by MeI yields phosphanylphosphido complexes [(2,6-i-Pr2C6H3N)2W(X)(1,2-η-t-Bu2PvP–CH3)] (X = Cl, I) (2-Cl/2-I) with the formation of a new P–C bond. Moreover, 1 reacts with electrophilic compounds [(OC)5M·THF] (M = Cr, Mo, W) to yield a series of novel dinuclear phosphanylphosphinidene complexes [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2PvP–M(CO)5)]Li·3DME (3, 4, 5) with very long P–M distances. Adducts [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2PvP–MCl3)] Li·3DME (6, 7) formed by reaction of 1 with GaCl3 and AlCl3 are labile and dissociate into 1 and MCl3 (M = Ga, Al). The outcomes of reactions were monitored by 31P-NMR spectroscopy. Furthermore, the structures of the isolated complexes 2-Cl/2-I, 3, 4, and [(2,6-i-Pr2C6H3N)2(Cl)W(1,2-η-t-Bu2PvP–W(t-Bu2PH)(CO)3COLi·2DME] (5-P) were confirmed unambiguously by X-ray diffraction studies.

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Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
DALTON TRANSACTIONS no. 45, edition 5, pages 2172 - 2179,
ISSN: 1477-9226
Language:
English
Publication year:
2016
Bibliographic description:
Grubba R., Ordyszewska A., Ponikiewski Ł., Gudat D., Pikies J.: An investigation on the chemistry of the R2P=P ligand: reactions of a phosphanylphosphinidene complex of tungsten(VI) with electrophilic reagents// DALTON TRANSACTIONS. -Vol. 45, iss. 5 (2016), s.2172-2179
DOI:
Digital Object Identifier (open in new tab) 10.1039/c5dt03085d
Verified by:
Gdańsk University of Technology

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