Chemistry of vinylidene complexes

Use of the MnCC system in organometallic and organic synthesis

“…The rearrangement 1a → 1 (reaction (3b) in Scheme 1) is best catalyzed by HMTA, when added to the UV irradiated mixture of CpMn(CO) 3 and PhC CH [46].…”

“…The main product of the reaction between Cp(CO) 2 Mn C CHPh (1) and (-H) 2 Os 3 (CO) 10 was the dark-red tetranuclear cluster CpMnOs 3 (-CH CHPh)(-H)(-CO)(CO) 11 (94, 60%) [126,127]. Simultaneously, the trinuclear clusters Os 3 ( 3 -C CHPh)(CO) 9 (95), (-H) 2 Os 3 ( 3 -CH CPh)(CO) 9 (96) and (-H)Os 3 (-CH CHPh)(CO) 10 (97) were isolated in 5-10% yields (Scheme 23, reaction (46)).…”

“…Contrary to Cp 2 (CO) 4 MnRe(-C CHPh) (47) (1) and (Acac)Rh(CO) 2 or (Hfac)Rh(CO) 2 , respectively (reaction (16) in Scheme 10) [26,27].…”

“…Thus, reaction (23), Scheme 12 resulted in replacement of the [Rh(Acac)(CO)] fragment by [Fe(CO) 4 ] [27]. Reactions (26), Scheme 13 led to the replacement of L at the Pt atom by CO [93]. The action of Fe 2 (CO) 9 on Cp(CO) 2 MnPt(-C CHPh)(dppe) (59) gave the tetranuclear 4 -vinylidene cluster (dppe)PtFe 3 ( 4 -C CHPh)(CO) 9 (82) [34] (see Section 5.2.1).…”

“…Addition of the coordinatively unsaturated [M L n ] fragments to the M C CHR system (A) became a common method of synthesis of the dinuclear heterometallic -vinylidene complexes with the central MM (-C CHR) fragment (B) [2]. Dozens of -vinylidene complexes with Mn M, Rh M, Os M bonds (M = Mo, W, Mn, Fe, Rh, Pd, Pt, Cu) were obtained by this method by the groups of Kolobova in Moscow, of Werner in Würzburg and in our group in Krasnoyarsk [21][22][23][24][25][26][27][28][29][30].…”