Simultaneous formation of new PdFe3 and MnFe2 clusters in the reaction of Cp(CO)2MnPd(μ−C=CHPh)(Ph2PCH2CH2PPh2) with Fe2(CO)9

Abstract

We have shown previously l'z that reactions of .u-vinylidene complexes Cp(CO);MnPt(I~-C=CHPh)I-,2 with iron nonacarbonyl can occur via two alternative routes depending on the nature of ligands L. When L = PPh3, the addition of the [Fe(CO)4] to vinylidene results in the formation of the trinuclear MnFePt la3-vinylidene cluster, l When L2 = Ph2PCH~_CH2PPh2 (dppe), the [Mn(CO)2CP] fragment is replaced by {Fe(CO)4] to form the tetranuclear PtFe3-~4-vinylidene cluster, z In continuation of the systematic studies in this area, we synthesized the first ~-vinylidene complex with the Mn--Pd bond (2) from Cp(CO)2Mn=C=CHPh (1) and Pd(PPh3) 4. (1,1-Dicarbonyl)(l-qS-cyclopentadienyl) ( 1,2-ls-phenylvinylidene) [2-rl2-bis(diphenylphosphino)ethane]manganesepalladium (3) was obtained by the replacement of the PPh 3 ligand by dppe. 3 In this work, we report on the results of studying the reaction of 3 with Fe2(CO) 9.The reaction of cluster 3 with Fe2(CO) 9 (benzene, 20 ~ 4 h) results in a mixture of products, which were isolated and characterized by the elemental analysis data and IR and NMR spectra. Three new clusters were obtained: (1,t,l,2,2,2,3,3,3-nonacarbonyl)-/a4-[ 1 -rl2,2,3,4-rl 1-(phenyl)ethenylidene]-[4-q2-bis(diphenylphosphino)ethane-PP" ]-bis( triangulo) (4) (green crystals, yield 9%),

Use of the MnCC system in organometallic and organic synthesis

“…Two parallel and competitive transmetalations of the MnPd(-C 1 C 2 HPh) system were observed in reactions with Fe 2 (CO) 9 (Scheme 25) [29,[36][37][38].…”

“…the transmetalation of Cp(CO) 2 MnPd(-C CHPh)( 2 -P-P) (64, 65) with Fe 2 (CO) 9 [29,36,37] and, in low yield, by addition of two Fe-carbonyl groups to Cp(CO) 2 Mn C CHPh (1) [37] (Scheme 21).…”

“…Distinctions between the chemical behaviour of Cp(CO) 2 MnPd(-C CHPh)(L 2 ) (L 2 = (PPh 3 ) 2 , dppm, dppe, dppp) and their MnPt analogues revealed by their reactions with Fe 2 (CO) 9 [29,[36][37][38]99], are briefly considered in this section.…”

“…The first 4 -vinylidene clusters containing platinum [34a] and palladium [36] have been synthesized starting from the dinuclear complexes Cp(CO) 2 MnM(-C CHPh)(dppe) (M = Pt, Pd). Below, the formation, structure and spectroscopic characteristics of (P-P)MFe 3 ( 4 -C CHPh)(CO) 9 (P-P = dppe, dppp; M = Pt, Pd) are considered.…”

“…As a result, trimetal 3 -vinylidene complexes with triangular MnFePt frameworks and MnFePt chain [32,33] and a series of 4 -vinylidene PtFe 3 [33][34][35] and PdFe 3 [29,[36][37][38] clusters were synthesized. The possibility of transfer of the vinylidene from one metal (Mn) to another metal (Re), to the dinuclear (FePt) system and to cluster (Os 3 , PdFe 3 , PtFe 3 ) systems was shown for the first time.…”