Untitled

Use of the MnCC system in organometallic and organic synthesis

“…The Mn C 1 bond (1.874(5)Å) in 67 is the shortest and the declination of the Mn 1 -C 1 -C 2 system (157.2(4) • ) from linearity is the smallest among the MnM -vinylidene complexes (Table 4) [30] close to those of the initial complex 1. The 13 C NMR spectrum of 67 showed an unusually low field C 1 resonance (δ 317.05 ppm) ( Table 5).…”

“…Compound [Cp(CO) 2 MnCu(-C CHPh)(-Cl)] 2 (67) is the first -vinylidene complex with an M-Cu bond proven by X-ray analysis [30]. The structures of the known earlier complexes ( 6 -C 6 H 6 )(i-Pr 3 P)OsCu(-C CHPh)(Cl) [24a] and Cp(iPr 3 P)RhCu(-C CHR)(Cl) (R = H, Me, Ph) [24b], were not reliably determined.…”

“…We obtained dark green 67 from the reaction (19) (Scheme 10) between Cp(CO) 2 Mn C CHPh (1) and CuCl in a quantitative yield [30]. The molecule 67 (Fig.…”

“…Reactions (31)- (33) in Scheme 12 result in splitting of the Mn Cu and Cu C 1 bonds [30]. Treatment of 67 with PPh 3 affords 1, which reacts further to give 36.…”

“…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].…”