A cationic allenylideneruthenium(II) complex with two bulky hemilabile phosphine ligands

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

“…In contrast, Werner and co-workers produced an 18electron allenylidene ruthenium complex XIV containing a hemilabile phosphine; however, the OÀRu bond was probably too stable to be readily displaced by an alkene in olefin metathesis [278] (Scheme 69). Moise and Le Gendre introduced a titanium(iv)-containing phosphine and produced complex XV, which is analogous to precursor IX b and exhibits similar activity [279] (Scheme 69).…”

Highly Active Catalysts in Alkene Metathesis: First Observed Transformation of Allenylidene into Indenylidene via Alkenylcarbyne—Ruthenium Species

“…Whereas alkenylcarbyne osmium [11] complexes have been fully described, only two types of unstable dicationic alkenylcarbyne ruthenium intermediates were recently reported on the protonation of the corresponding allenylidene ruthenium complexes, [RuCl( CCH=CPh 2 )(k 2 -P,O-Cy 2 PCH 2 CH 2 OCH 3 )(k-P-Cy 2 PCH 2 CH 2 OCH 3 )][BF 4 ,PF 6 ] by Werner et al [12] and [Cp*Ru(dippe)( CCH = CPh 2 )] [B(Ar F ) 4 ] 2 by Valerga and co-workers. [13] No formation of related indenylidene complexes was observed in these examples.…”

“…Four doublets between d = 6.36 and 6.15 ppm were observed for the four arene protons of the coordinated p-cymene ligand. Attempts to isolate complex 3 were unsuccessful because of slow decomposition of the complex at room temperature by loss of p-cymene ligand and formation of [HPCy 3 [12] and [Cp*Ru(dippe)( CCH = CPh 2 )] [B(Ar F ) 4 ] 2 by Valerga and co-workers. [13] No formation of related indenylidene complexes was observed in these examples.…”

Reactions of Hydride Complexes of Ruthenium and Osmium with Propargylic Alcohols: Preparation of Chelate Vinyl ­Derivatives

“…Correspondingly, the bond angle C26-C39-C25 bends from 177 to 125.3(3)°. This results in a lower bond order in the vinyl ligand relative to that in the crystal structure of 1,1-diphenyl-2-propyl-1-ol alone [19] and that which is cocrystallised with a Ru II complex: [20] the C26-O13 bond is stretched from 1.430 Å in the free ligand (1.426 Å in the cocrystal) to 1.500(3) Å in 1a; C26-C39 changes from 1.476 (1.490) to 1.535(4) Å and C39-C25 from 1.168 (1.169) to 1.318(4) Å; C26-C27 and C26-33 are less affected and measure 1.530 and 1.530 Å in the free molecule (1.536, 1.537 Å cocrystal) and 1.544(3) and 1.539(4) Å in 1a. The Ru-O bond [2.232(2) Å] is also slightly longer than expected when compared with the bond length observed for a coordinated water molecule trans to a P(OEt 3 ) 3 ligand (2.218 Å).…”