Reactions of coordinated molecules. 50. The preparation of homo- and heterodinuclear complexes containing .mu.-alkenylidene ligands

Reactivity of Silylated Dinuclear Iron−Platinum Acyl Complexes: Formation of μ-Vinylidene Complexes and Crystal Structures of the Acyl Complex [(OC)3{(MeO)3Si}Fe(μ-dppm)Pt{C(O)Me}(t-BuNC)] and the μ-Vinylidene Complex [(OC)3Fe{μ-CC(H)Ph}(μ-dppm)Pt(PPh3)]

“…Similar chemical shifts and couplings have been reported by Antonova et al for phenylethenylidenebridged heterobimetallics of the type [(OC) 2 CpMn{µ-CdC(H)Ph}Pt(PR 3 ) 2 ] 22,23 and by Lukehart for the cationic complex [(OC)CpFe(µ-CO){µ-CdC(H)Ph}Pt(PEt 3 ) 2 ] [PF 6 ]. 24 The 13 C{ 1 H} NMR spectrum recorded at ambient temperature displayed broad resonances in the carbonyl region and in the range expected for the R-vinylidene carbon atom. More informative was the spectrum recorded at 253 K. A sharp doublet of doublets for the R-vinylidene carbon atom with 2 J(P-C) couplings of 11 and 58 Hz was now observed at δ 238.5.…”

“…35 The same orientation has been suggested for [(OC) 2 CpMn{µ-CdC(H)Ph}Pt(PR 3 ) 2 ] 23 and for [(OC)-CpFe(µ-CO){µ-CdC(H)Ph}Pt(PEt 3 ) 2 ][PF 6 ]. 24 For compounds 6, however, the relative orientation of the bridging vinylidene ligand cannot be predicted with certainty.…”

Use of the MnCC system in organometallic and organic synthesis

“…Complexes of the "A-frame" type X 2 MPd(-C CR 2 )(-dppm) 2 (X = Cl, Br, I; M = Ni, Pd; R = H, Cl) [4,96] and the cationic complex [(PhC C)PdPt(-C CHPh)(PEt 3 ) 4 ] + [97] were the only palladium-containing vinylidene complexes reported before our work [28]. The -carbene complex Cp(CO) 2 MnPd[-C(OMe)Ph](PMe 3 ) 2 had also been described [98].…”

Chemistry of vinylidene complexes. XVI. Crystal and molecular structure of the novel tetranuclear μ2-μ3-bis-vinylidene complex (η2-dppe)PdMn(μ3-CCHPh)PdMn(μ-CCHPh)(CO)4Cp2

“…The addition of the [PtL 2 ] groups (L = PPh 3 , P(OR) 3 ) to Cp(CO) 2 Mn@C@CHPh (A) resulted in the formation of dimetal complexes Cp(CO) 2 MnPt(l-C@CHPh)L 2 (B) [4], the following reactions of which with Fe 2 (CO) 9 gave a series of trimetal clusters CpMnFePt(l 3 -C@CHPh)(CO) 6 L and CpMnFePt(l 3 -C@CHPh)(CO) 5 L 2 (C) [3]. The products of addition of ironcarbonyl fragment to Cp(CO) 2 MnPt(l-C@CHPh)(g 2 -dppm) (1) [5] were a triangular cluster CpMnFePt(l 3 -C@CHPh)(l-dppm)(CO) 5 (C) and its derivative CpMnFePt(l 3 -C@CHPh)(CO) 5 [g 1 -Ph 2 -PCH 2 P(@O)Ph 2 ] (2) with a metal core in the form of the Mn-Fe-Pt chain (C 0 ) [6] (see Scheme 1).…”

“…Only two types of vinylidene palladium derivatives, viz. ''A-frame'' complexes X 2 MPd(l-C@CR 2 )(l-dppm) 2 (X = Cl, Br, I; M = Ni, Pd; R = H, Cl) [8] without direct metal-metal bonds, as well as [(PhC"C)PdPt(l-C@CHPh)(PEt 3 ) 4 ] + [PF 6 ] À [9] 0022-328X/$ -see front matter Ó 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jorganchem.2006.12.012 q For Part XV, see Ref.…”