Chemistry of vinylidene complexes

Abstract

alnszitute of C/wmi~try and Chemical Technolo.gy, Siberian Branch of the Russian Academy ~/Sciences. 42 u/. K. ,$tarksa, 660049 Krasnoyarsk. Russian Federation. Fax: +7 (391 2) 2.] 8658. E-maih root@chem.krasnoyarsk.su #A. N. ,%esmeyanov Inslitute of Organoelemenz Compounds, Russian Academy of Sciences, 2S ul. Vavilova, 117S13 Moscow, Russian Federation. Fax: + 7 (095~ 135 5085.The reaction of Cp(CO)2Mn=C=CHPh (i} with Pd(PPhO-followed by the replacement of the PPh~ ligands by diphosphmes Ph2PICH2)2PPh 2 (dppe) or Ph2P(Ct-t2)3PPh 2 (dppp) (where dppe is bis(diphenylphosphino)ethane and dppp is 1,3-bisr afforded the binuclear complexes CplCO):MnPd(p*C=CHPh)(dppe) (2a) and Cp(CO):MnPd(~t-C=CHPh)(dppp) (2b), respectively. The reactions of 2a and 2b with Fe~(CO) 9 ga~e the trinuctear complex CpMnFe2(~B-C=CHPh)(CO)8 (37. Competitive transmetaHation took the second pathway to yield clusters containing the PdFe 3 and PdFe, cores. Complex 3 was also formed in the thermal reaction of compound I with I=e2{CO), ~. Complex 3 was studied by IR spectroscopy, IH and t3C NMR spectroscopy, massspectrometp/, and X-my diffraction analysis.

Use of the MnCC system in organometallic and organic synthesis

“…The C 1 C 2 bond in 89 (1.42(2)Å) is longer than that of triangular clusters, such as CpMnFe 2 ( 3 -C CHPh)(CO) 8 (91) (av. 1.31Å) [37] and Fe 3 ( 3 -C CHPh)(-CO)(CO) 9 (92) (1.38Å) [122]. The C 1 and C 2 atoms in 89 are almost equally distant from the Pt atom (Pt-C 1 2.24(1), 2.23(1)Å; Pt-C 2 2.24(1), 2.18(1)Å).…”

“…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).…”

“…Treatment of 1 with Fe 2 (CO) 9 at 20-90 • C affords 4 -[Cp(CO) 2 MnC(CO)CHPh]Fe(CO) 3 (51) solely (Section 3.3) [37,90]. The sharp contrast between the conditions required for the formation of 91 from 1 (98 • C, 10%) and from 64 (20 • C, 71%) suggests a specific role of palladium in the easy formation of 91 in reaction (44).…”

“…Reactions (17) in Scheme 10 between Cp(CO) 2 Mn C CHPh (1) and PtL 4 were used to form Cp(CO) 2 MnPt(-C CHPh)(L) 2 (L = P(OEt) 3 (37), PPh 3 (52), P(OPh) 3 (53) Complexes 52-55 are practically inert to the action of CO gas. The use of Co 2 (CO) 8 as a source of CO allowed the tricarbonyl complexes 56 and 57 in good yield (reactions (26)).…”

“…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.…”