(C5Me5)Ru-vinylidene complexes from terminal alkynes and propargyl alcohol derivatives

Further reactions of some bis(vinylidene)diruthenium complexes

“…It was identified by comparison with the literature [17], with m(CO) at 1972 cm À1 and NMR resonances at d H 1.66 (Cp*) and d C 10.20 (Cp*-Me), 100.05 (Cp*-ring) and 203.31 (CO). Similar oxidations of Ru(II) vinylidenes to give carbonyl cations have previously been reported and in some cases aldehyde by-products isolated [10,[18][19][20][21]. An alternative synthesis of 9 was by the direct reaction of 1 with [NH 4 ]PF 6 in MeOH under an atmosphere of CO.…”

“…The two Ru-P distances are slightly longer than in RuCl(dppm)Cp* [2.2882(5), 2.2812(4) Å ] [3b] and reflect the reduced back-bonding from the cationic ruthenium centre to the phosphorus nuclei. The carbonyl group has similar Ru-C and C-O bond lengths to those found in related complexes [20,22].…”

Preparation and reactivity of diazoalkane complexes of ruthenium stabilised by an indenyl ligand

“…However, the phenyl ring and vinylidene units are not coplanar, contrasting with the planar RuvCvCHR moiety found in the above-mentioned complexes. [29][30][31] Therefore, if the plane of the phenyl ring is considered (r.m.s. deviation of 0.0072 Å), in 9d the C(2) atom is coplanar [deviated by 0.011(2) Å] but C(1) is deviated by 0.55(3) Å and the ruthenium atom lies at 1.20(4) Å from the plane.…”

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

“…[136,[145][146][147] Therefore the intermediacy of vinylidenes cannot be excluded in the conversion of alkynyl radical cations into carbonyls. However, these reactions are generally slow and a growing body of evidence points to more direct hydrolysis mechanisms that may occur on faster timescales.…”