717110-27-5Relevant academic research and scientific papers
Lithiation of diynyl-ruthenium complexes: Routes to novel metallated functional diynes
Bruce, Michael I.,Scoleri, Nancy,Skelton, Brian W.
, p. 3473 - 3482 (2011/10/30)
Conditions for the efficient lithiation of the diynyl group in complexes Ru(CCCCH)(PP)Cp′ [(PP)Cp′ = (dppe)Cp (*) 1, (PPh 3)2Cp 2 have been investigated. Addition of two equiv. LiBu to the diynyl complexes in thf solution at -78°C effects rapid conversion to putative Ru(CCCCLi)(PP)Cp′. Assays using subsequent reactions with either SiClMe3 or AuCl(PPh3) indicate that up to 80% conversion can be achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)OMe, PhCHO, Ph 2CO and metal-containing substrates [MClPh3 (M = Ge, Sn), trans-RhCl(CO)(PPh3)2, cis-PtCl2(PPh 3)2, CuCl(PPh3), (AuCl)2(μ-dppm) proceed to give functionalised diynyl complexes or bimetallic derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-ray diffraction molecular structures of Ru(CCCCR)(dppe)Cp (*) (R = Me, GePh3) are reported: there is significantly greater delocalisation along the Ru-C4-R chain in the GePh 3 derivative.
Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium
Bruce, Michael I.,Ellis, Benjamin G.,Gaudio, Maryka,Lapinte, Claude,Melino, Giovanni,Paul, Frederic,Skelton, Brian W.,Smith, Mark E.,Toupet, Loic,White, Allan H.
, p. 1601 - 1609 (2007/10/03)
Reactions between HC≡CC≡CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C≡CC≡CSiMe 3)(L2) Cp′ [Cp′ = Cp, L = CO (1), PPh 3 (2); Cp′ = Cp*, L2 = dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-y1 complexes Ru(C≡CC≡CH)(L2) Cp′ [Cp′ = Cp, L = PPh3 (5); Cp′ = Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3) 2 to give Ru(C≡CC≡CAu(PR3)}(L 2)Cp′ [Cp′ = Cp, L = PPh3, R = Ph (7); Cp′ = Cp*, L2 = dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped {Cp(Ph3P)2Ru} C≡CC≡C{Ru(dppe)Cp*} (10) was obtained from Ru(C≡CC≡CH)(dppe)Cp′ and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of 1-3 and 6-9 are reported, with a comparative determination of the structure of Fe(C≡CC≡CSiMe 3)(dppe)Cp′ (4), and those of a fifth polymorph of {Ru(PPh 3)2Cp}2(μC≡CC≡C) (12), and {Ru(dppe)Cp}2(μ-C≡CC≡C) (13).
