188885-87-2Relevant academic research and scientific papers
Hemilabile properties of the η3-diphenylvinylphosphine (DPVP) phosphaallyl ligand: Synthesis and reactions of [(η5-C5Me5)Ru(η 3-DPVP)(η1-DPVP)]PF6
Barthel-Rosa, Luis P.,Maitra, Kalyani,Fischer, Jean,Nelson, John H.
, p. 1714 - 1723 (2008/10/08)
Pentamethylcyclopentadienyl-ruthenium(II) half-sandwich complexes containing the olefinic phosphine ligand diphenylvinylphosphine (DPVP) are described. The hemilabile properties of the η3-DPVP ligand, a neutral monometallic phosphaallyl, are illustrated by reactions with carbon monoxide and terminal acetylenes. DPVP reacts with [(η5-C5Me5)-RuCl2]2 to give the disubstituted ruthenium(II) compound [(η5-C5Me5)Ru-(η 3-DPVP)(η1-DPVP)]-PF6 (1). 1 reacts with NaNCS to form [(η5-C5Me5)Ru(η1-DPVP) 2(NCS)] (2). 1 reacts with CO, HC≡CPh, HC≡CCH2CH2OH, and HC≡CCH2OH to form [(η5-C5Me5)Ru(η1-DPVP) 2(CO)]PF6 (3), [(η5-C5Me5)Ru(η1-DPVP) 2{C=C(H)(Ph)}]PF6 (4), [(η5-C5Me5)Ru(η1-DPVP) 2{C(CH2)3O}PF6 (5), and [(η5-C5Me5)Ru(η1-DPVP) 2{C=C(H)(CH2OH)}]PF6 (6), respectively. 6 slowly decomposes in aerated solutions to form 3, presumably through an allenylidene intermediate. 6 reacts with excess DPVP and HPF6 to form the novel, P,P-diphenyltrihydrophospholonium vinylidene compound [(η5-C5Me5)Ru(η1-DPVP) 2{C=C(CH2)2PPh2CH 2}][PF6]2 (7). The characteristic 1H, 13C{1H}, and 31P{1H} spectroscopic features of all compounds are described. The molecular structures of compounds 1, 4, 5, and 7 have been determined by single crystal X-ray crystallography.
