Jump to main content
Jump to site search

Issue 5, 2016
Previous Article Next Article

An investigation on the chemistry of the R2P[double bond, length as m-dash]P ligand: reactions of a phosphanylphosphinidene complex of tungsten(VI) with electrophilic reagents

Author affiliations

Abstract

The nucleophilic properties of the title compound [(2,6-i-Pr2C6H3N)2(Cl)W(η2-t-Bu2P[double bond, length as m-dash]P)]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-Bu2P[double bond, length as m-dash]P–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-Bu2P[double bond, length as m-dash]P–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-Bu2P[double bond, length as m-dash]P–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-Bu2P[double bond, length as m-dash]P–W(t-Bu2PH)(CO)3COLi·2DME] (5-P) were confirmed unambiguously by X-ray diffraction studies.

Graphical abstract: An investigation on the chemistry of the R2P [[double bond, length as m-dash]] P ligand: reactions of a phosphanylphosphinidene complex of tungsten(vi) with electrophilic reagents

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Aug 2015, accepted on 29 Oct 2015 and first published on 30 Oct 2015


Article type: Paper
DOI: 10.1039/C5DT03085D
Citation: Dalton Trans., 2016,45, 2172-2179
  •   Request permissions

    An investigation on the chemistry of the R2P[double bond, length as m-dash]P ligand: reactions of a phosphanylphosphinidene complex of tungsten(VI) with electrophilic reagents

    R. Grubba, A. Ordyszewska, Ł. Ponikiewski, D. Gudat and J. Pikies, Dalton Trans., 2016, 45, 2172
    DOI: 10.1039/C5DT03085D

Search articles by author

Spotlight

Advertisements