Ru(xantsil)(CO)(PCy₃):  Facile Generation of a Coordinatively Unsaturated Ruthenium(II) Complex Bearing 14 Valence Electrons [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)]

Abstract

Treatment of Ru(xantsil)(CO)(η6-toluene) (1) [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)] with PCy3 led to the formation of Ru(xantsil)(CO)(PCy3) (3), in which the xantsil ligand is bound to the ruthenium center in κ3(Si,Si,O) fashion. The highly coordinatively unsaturated nature of 3 is indicated by the reaction with CO to give Ru(xantsil)(CO)3(PCy3) (5).

A Surprising Reaction of Trimethylphosphane with the Unsaturated Diruthenium Complex [(η6‐C6Me6)2Ru2(μ2‐H)3]+: Synthesis and Molecular Structure of the Cations [(η6‐C6Me6)Ru2(PMe3)3(μ2‐H)3]+ and [(η6‐C6Me6)2Ru2(PMe3)2(μ2‐H)(H)2Tschan1, Cherioux2, Therrien3 et al. 2007Eur J Inorg Chem6120View full textAdd to dashboardCite

“…Cation 1 is obtained in 28 % yield and it can be isolated as the tetrafluoroborate salt (Scheme 1). The substitution of an η 6 -arene ligand at a ruthenium atom by three phosphane ligands has been observed so far for benzene, [4] toluene [5] and pcymene [6] ligands, but never for the strongly bound η 6 -C 6 Me 6 ligand. The single-crystal X-ray structure analysis of [1][BF 4 ], crystallised by slow diffusion of diethyl ether in a concentrated acetone solution of [1][BF 4 ], reveals for cation 1 the presence of three bridging hydrido ligands coordinated to the two ruthenium atoms, one ruthenium atom being coordinated to an η 6 -C 6 Me 6 ligand and the other one to three PMe 3 ligands.…”

Activation of Mononuclear Arene Ruthenium Complexes for Catalytic Propargylation Directly with Propargyl Alcohols

“…As an attempt to provide a higher stability to the catalytic intermediates, the complex [(p-cymene)Ru- [22] considered as a 14-electron synthetic equivalent. The release of the arene ligand is also described in analogous ruthenium complexes of type [(h [23] and it is proposed as the initial step towards the generation of the olefin metathesis catalytically active species from [(h…”

New hydrosilylation reaction of arylacetylene accompanied by C-H bond activation catalyzed by a xantsil ruthenium complex

“…The coordinatively unsaturated ruthenium xantsil phosphine complex 1 was synthesized via three reaction steps illustrated in Scheme 1 from Ru 3 (CO) 12 and the ligand precursor xantsilH 2 (2) [7,8]. The reaction of Ru 3 (CO) 12 and 2 in toluene at 120 °C for 90 min afforded tetracarbonyl xantsil complex cis-Ru{κ 2 (Si,Si)-xantsil}(CO) 4 (3) in 35 % yield.…”

“…Complex 3 was then heated in refluxing toluene for 5 h to give the η 6 -toluene complex Ru{κ 2 (Si,Si)-xantsil}(CO)(η 6 -toluene) (4) in 95 % yield by substitution of three carbonyl ligands with a toluene molecule [7]. The η 6 -toluene ligand in 4 is substitution labile and can be substituted cleanly with various ligands at room temperature [8]. We have found that the reaction of 4 with a bulky tricyclohexylphosphine resulted in substitution of one phosphine molecule (2-electron donor) for a toluene ligand (6-electron donor) to give complex 1 [8].…”

“…Several years ago, we developed a bis(silyl) chelate ligand xantsil [(9,9-dimethylxanthene-4,5diyl)bis(dimethylsilyl)] based on a xanthene backbone ( Fig. 1) [7,8]. The xantsil ligand has several unique features: (i) xantsil is a rigid chelate ligand, and the chelate effect prevents the easy elimination of silyl groups; (ii) the wide Si-M-Si bite angle prevents the Si-Si reductive elimination; (iii) the silyl ligands work as strong σ-donors with high trans influence; and (iv) the weak M-O dative bond can sta-bilize coordinatively unsaturated metal center.…”