title: 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(η(2)-t-Bu2P = 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 = 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 = 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 = 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 (31)P-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 = P-W(t-Bu2PH)(CO)3COLi·2DME] (5-P) were confirmed unambiguously by X-ray diffraction studies.
authors.affiliation: Chemical Faculty, Department of Inorganic Chemistry, Gdansk University of Technology, G. Narutowicza St. 11/12, Pl-80-233 Gdansk, Poland. grubba@pg.gda.pl jerzy.pikies@pg.gda.pl.
authors.forename: Rafał
authors.initials: R
authors.lastname: Grubba
authors.forename: Anna
authors.initials: A
authors.lastname: Ordyszewska
authors.forename: Łukasz
authors.initials: Ł
authors.lastname: Ponikiewski
authors.forename: Dietrich
authors.initials: D
authors.lastname: Gudat
authors.forename: Jerzy
authors.initials: J
authors.lastname: Pikies