403607-77-2Relevant academic research and scientific papers
Deactivation of ruthenium metathesis catalysts via facile formation of face-bridged dimers
Amoroso, Dino,Yap, Glenn P.A.,Fogg, Deryn E.
, p. 3335 - 3343 (2002)
Reaction of RuCl(dcypb)(μ-Cl)3Ru(dcypb)(N2) (3) with an excess of tert-butylacetylene at ambient temperatures yields the dinuclear monovinylidene RuCl(dcypb)(μ-Cl)3Ru(dcypb)(L) (4a; L = C=CHBut, dcypb = 1,4-bis(dicyclohexylphosphino)butane), rather than the expected mononuclear RuCl2(dcypb)(L). Attempted synthesis of an allenylidene derivative via the corresponding reaction with 1,1-diphenyl-2-propyn-1-ol stops at the stage of hydroxyvinylidene 4b (L = C=CHC(OH)Ph2). While formation of these dinuclear products may be an artifact of low solubility, the corresponding monoalkylidene species 4c (L = CHCH=CMe2) is obtained on treating soluble RuH(dcypb)(μ-Cl)2(μ-H)Ru(dcypb)(H2) (5) with 3-methyl-3-chloro-1-butyne. Formation of the perchloro species 4c is consistent with facile homodimerization of the initially formed RuCl2(dcypb)(CHCH-CMe2) (2d), with expulsion of one alkylidene ligand as the free carbene. 2,7-Dimethylocta-2,4,6-triene, the formal product of carbene coupling, is observed by 1H NMR. A minor product in this synthesis is proposed to be RuCl(dcypb)(μ-Cl)2(μ2,η1-CHCH=CMe 2)RuCl(dcypb) (8). While the low activity of 4a/4b in ring-opening metathesis polymerization of norbornene is attributable to their low solubility, that of 4c points toward the stability of the Ru2(μ-Cl)3 entity. The low activity and facile formation of 4c reveals an important deactivation pathway for catalysts of type 2d, with additional relevance to other such chlororuthenium complexes, including systems of the Grubbs type. Product identities were established by 1H, 2H, 13C, and 31P NMR and IR spectroscopy and (for 4c and 5) by X-ray crystallography.
A stable silylene in a reactive environment: Synthesis, reactivity, and silicon extrusion chemistry of a coordinatively unsaturated ruthenium silylene complex containing chloride and η3-P-C-P ligands
Amoroso, Dino,Haaf, Michael,Yap, Glenn P.A.,West, Robert,Fogg, Deryn E.
, p. 534 - 540 (2008/10/08)
Reaction of [(dcypb)ClRu(μ-Cl)3Ru(dcypb)(N2)] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-l,3,2-diazasilol-2-ylidene (SiL2N) yields coordinatively unsaturated RuCl(η3-dcypb)(SiL2/s
