Synthesis of new half-sandwich ruthenium(II) complexes bearing alkenyl- and alkynylphosphane ligands

Carbonyl substitution of the complex [RuI(eta(5)-C9H7)(CO)(2)] with the activated phosphanes Ph2PR (R = CH2CH CH2, CH2CH2CH=CH2, and C CPh) affords the complexes [RuI(eta(5)-C9H7)(CO)(Ph2PR-kappa P)] [R = CH2CH=CH2 (1a), CH2CH2CH=CH2 (1b), C CPh (1c)]. The reaction of the complex [RuCl(eta(5)-C9H7)(PPh3)(2)] with the corresponding phosphanes, in refluxing THF, gives the complexes [RuCl(eta(5)-C9H7)(PPh3)(Ph2PR-kappa P)] [R = CH2CH2CH=CH2 (2b), C CPh (2c)] by substitution of PPh3. The cationic derivatives [Ru(eta(5)-C9H7)(L)(Ph2PR-kappa(3)P,C,C)] [X] [L = CO, X = SbF6, R = CH2CH=CH2 (3a), CH2CH2CH=CH2 (3b); L = PPh3, X = PF6, R = CH2CH2CH=CH2 (4b)] have been prepared by treatment of the complexes 1a,b and 2b with a halide abstractor such as AgSbF6 or NaPF6, respectively. Deprotonation reactions of the complexes 3b and 4b with cesium carbonate have been carried out, giving rise to the neutral complexes [Ru(eta(5)-C9H7)-(L)(Ph2PCH2CH=CHCH2-kappa(2)P,C)] [L = CO (5a), PPh3 (5b)]. The reaction of complex 3a with MeCN generates the complex [Ru(eta(5)-C9H7)(MeCN)(CO)(Ph(2)pCH(2)CH=CH2-kappa P)][SbF6] (6). The vinylidene [Ru(eta(5)-C9H7)(PPh3)(Ph2PC CPh-kappa P){C=C(Ph)H}][PF6] (7) and allenylidene [Ru(eta(5)-C9H7)(PPh3)- (Ph2PC CPh-kappa P)(C=C=CPh2)][PF6](8) derivatives have been synthesized by reaction of complex 2c with phenylacetylene or 1,1-diphenylprop-2-yn-l-ol, respectively. The structures of the derivatives 1c, 3a, and 4b have been determined by single-crystal X-ray diffraction analysis.