Reaction of 1,3-diynes with the electron rich iron complex (η5-C5Me5)(η2-dppe)FeCl. A new and direct access to the iron butadiynyl complex (η5-C5Me5)(η2-dppe)FeCCCCSiMe3

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

“…All three monoruthenium complexes Ru(C∫CPh)(PP)Cp¢ have been reported elsewhere. 8,23,24 Of the diruthenium complexes only the very insoluble compound 1,4-{Cp(PPh 3 ) 2 RuC∫C} 2 C 6 H 4 (11)has been prepared previously. 25 The more soluble systems 1,4-{Cp(dppe)RuC∫C} 2 C 6 H 4 (12) and 1,4-{Cp*(dppe)RuC∫C} 2 C 6 H 4 (13) were readily prepared from reactions of 1,4-(Me 3 SiC∫C) 2 C 6 H 4 and two molar equivalents of the appropriate chloride precursor RuCl(PP)Cp¢ in the presence of KF (Scheme 3).…”

“…Recent studies of the redox properties of the alkynyl systems M(C∫CAr)(PP)Cp¢ [M = Fe, Ru, Os; PP = (PPh 3 ) 2 , dppe; Cp¢ = Cp, Cp*] groups, 7-9 together with the growing spectrum of synthetic methods available for the preparation of organometallic compounds featuring alkynyl-based ligands, including in situ desilylation/metalation 10, 11 and palladium and/or coppercatalysed cross-couplings within the metal-ligand sphere, 8,12-15 have led us to reconsider the synthetic chemistry of some fluorinated analogues. Below we describe the syntheses of a variety of complexes containing perfluorinated phenyl and phenylene ring systems that illustrate the use of in situ desilylation/metallation protocols and gold-enhanced cross-coupling reactions in the preparation of organometallic derivatives of pentafluorophenylacetylene and 1,4-diethynyltetrafluorobenzene.…”

20 Organometallic chemistry of monometallic species

“…178 A new and direct access to the iron butadiynyl complex [Fe(C᎐ ᎐ ᎐ CC᎐ ᎐ ᎐ CSiMe 3 )(η-C 5 Me 5 )(η 2 -dppe)] has been reported, via the reaction of a 1,3-diyne with the electron rich [FeCl-(η 5 -C 5 Me 5 )(η 2 -dppe)]. 179 Iminosemiquinonate ligands (apR) form from the deprotonation reaction of 2-arylazo-4-methylphenol that occurs upon complexation to Os in [Os(PPh 3 ) 2 -(apR)Br] 33; the apR ligand coordinates to osmium as a tridentate C,N,O donor ligand forming a five-membered chelate. 180 The complex [Ru(Cp*)Cl(PPh 3 ) 2 ] has been found to be a versatile catalyst for living radical polymerization of methyl methacrylate (MMA), methyl acrylate (MA), and styrene (St) with Al(OPr i ) 3 as an additive.…”

Heptahexaenylidene Complexes: Synthesis and Characterization of the First Complexes with an MCCCCCCCR2 Moiety (M = Cr, W)

“…Since then, a few other butatrienylidene complexes of iridium and manganese have been isolated or at least spectroscopically characterized in solution. Several cationic butatrienylidene complexes of ruthenium and iron were generated in solution by the groups of Selegue, Bruce, Winter, Dixneuf, and Lapinte . Due to the very high reactivity of these complexes, they could be neither isolated nor spectroscopically detected and therefore were only trapped with nucleophiles.…”