Chemistry of vinylidene complexes. V. The ligand substitution reactions at the platinum atom in complexes Cp(CO)2MnPt(μ-CCHPh)L2

Use of the MnCC system in organometallic and organic synthesis

“…The equilibrium between 62 and 63 did not shift to the right by the addition of an excess of dppm. Stepwise substitution was observed [93] for monodentate ligands PR 3 at the Pt atom (reactions (24) and (25) in Scheme 13). However, we failed to isolate any complexes containing "dangling" 1 -P-P ligands in reactions (27) (Scheme 13), (29) and (30) (Scheme 14).…”

“…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).…”

“…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). It is likely that the above reactions occurred through corresponding trimetal MnFeRh, MnCoPt or MnFePt intermediates (type Z, Scheme 19) [35,93].…”

“…The -vinylidene MnPt complexes react with phosphines and phosphites without cleavage of the cycle (Scheme 13)[93,94]. The reaction (24) between Cp(CO) 2 MnPt(-C CHPh)(PPh 3 ) 2 (52) and P(O-i-Pr) 3 occurred in two consecutive stages[93]. With one eq., the mixed-ligand com-plex Cp(CO) 2 MnPt(-C CHPh)[P(O-i-Pr) 3 ](PPh 3 ) (54) was formed, while an excess of phosphite gave Cp(CO) 2 MnPt(-C CHPh)[P(O-i-Pr) 3 ] 2 (55).…”

Chemistry of vinylidene complexes. XXIV. A new μ-vinylidene complex containing RePt core, and platinum-bound carbonyl ligand. Spectroscopic, structural and electrochemical study

“…Another route to the heterobimetallic complexes with the platinum-bound CO ligands is ligand exchange reactions [19,20]. Such ligand exchange can be performed in two main ways: by a treatment of the initial complex with gaseous carbon monoxide [20,21], or by a reaction of one with metal carbonyl compounds [19,22,23]. It should be noted that the carbon monoxide can initiate a cleavage of metal-metal bond and lead to decomposition of starting compound, for example, reactions of µ-carbene complexes with CO lead to formation of triangular clusters containing Pt 3 cores [24][25][26].…”