Synthesis and reactivity of cationic vinylidene and allenylidene ruthenium(II) complexes containing the phosphinoether Prⁱ₂PCH₂CH₂OMe as chelating ligand

Abstract

An efficient method for the preparation of the chelate complex [R~C~,(K~P,O-P~',PCH,CH,OM~),] 2, using [(RuC~,(C,H,,)},] 1 as starting material, has been developed. Compound 2 reacts with terminal alkynes HC=CR (R = Ph, C6H4Me-p or C6H4C=cH-m) in the presence of Ag(O,SCF,) to give the octahedral cationic vinylidene complexes [R~C~(=CSHR)(K~P,O-P~',PCH~CH,OM~),][O,SCF,] 4-6 in 70-80% yield. The parent derivative 3 (R = H) has been prepared analogously but is stable only under an acetylene atmosphere. Crystal structural analysis of 4 (R = Ph) confirms a cis arrangement of the chloro and vinylidene ligands. Treatment of 4 with basic Al,O, produces, by deprotonation, a mixture of two isomers [RuCI(C=CPh)(K'P,O-Pri,PCH2CH,0Me),] 7 , 8 with the alkynyl and chloro ligands in either cis or trans disposition. Compounds 7 , 8 easily react by partial cleavage of the chelate bonds to give the corresponding dicarbonyl derivatives

Formation of a Ruthenium μ‐Carbide Complex with Acetylene as the Carbon Source

“…The structures of 5 and 6 can be described as face‐bridged dimers with a ( p ‐cymene)Ru fragment connected by three chlorido bridges to a RuCl(=C=CHR)(PCy 3 ) fragment 6. The Ru1–C1 distances [1.817(6) Å for 5 ; 1.778(8) Å for 6 ] are comparable to those of other coordinatively saturated Ru–vinylidene complexes such as [TpRuCl(=C=CHPh)(PPh 3 )] [1.801(4) Å]7 or [{RuCl( i Pr 2 PCH 2 CH 2 OMe) 2 (=C=CHPh)}(OTf)] [1.790(3) Å] 8. Apart from the vinylidene ligand, the bond lengths for 5 and 6 are similar to those for the starting material 4 .…”

Preparation and reactions of some neutral pentamethylcyclopentadienylruthenium vinylidene complexes

“…A small amount of 2 was also obtained. 13 C NMR resonance at δ 336.38, the latter by a crystal structure determination (see below). Other spectroscopic data were consistent with these structures and are detailed in the Experimental section.…”

Hemilabile Properties of the η3-Diphenylvinylphosphine (DPVP) Phosphaallyl Ligand: Synthesis and Reactions of [(η5-C5Me5)Ru(η3-DPVP)(η1-DPVP)]PF6

“…Hybrid ligands are those ligands containing two or more chemically different atoms or groups of atoms suitable for coordination to a metal center. In addition, hybrid ligands frequently contain functionalities that display hemilabile properties. Hemilabile atoms or groups of atoms can reversibley create or occupy a vacant coordination site on a transition metal center.…”