abstracts - Институт катализа им. Г.К. Борескова

OP-II-1elucidation of the mechanism (Scheme 3) and energy profile (see an example in Figure 1) ofproton transfer to and from transition metal hydride complexes via hydrogen bondedintermediates. The important role of hydrogen bonded ion pairs [M(η 2 -H 2 )] + …X - in thestabilization of dihydrogen complexes was shown. The influence of media properties on thekinetics and thermodynamics of the proton transfer was studied. Two possible pathways forfurther transformation of (η 2 -H 2 ) hydrides: isomerization into classical polyhydride and H 2substitution by another ligand, such as X - , CO, N 2 etc – will be discussed.Figure 1. Experimental energy profile (ΔH) for the reaction of Cp*FeH(dppe) with HFIP.-6.5±0.4kcal mol -1 2.6±0.3kcal mol -1 -4.2±1.2kcal mol -117.0±0.5kcal mFe HPh 2PPPh 2F +3CCHOHF 3CPh 2PFe HPPh 2HOCHF 3CCF 3Ph 2P+HFeHPPh 2OF 3CCHCF 3F 3CCHH O-CF 3kcal mol -1 ?+FeF 3CHHPh 2PCHPPh 2OH OCHF 3CCF 3-CF 3We are grateful to the HYDROCHEM program (Project RTN n° HPRN-CT-2002-00176), Division of Chemistry and Material Science of RAS and RFBR (05-03-32415, 05-03-22001) and CNR-RAS bilateral agreement for the support of this workReferences:1 Recent Advances in Hydride Chemistry (Eds.: M. Peruzzini, R. Poli), Elsevier,Amsterdam, 2001.2 Reversible protonation of cis-[FeH 2(dppe) 2] by alcohols to yield trans-[FeH(H 2)(dppe) 2 ] +was first reported by M.V. Baker, L. D. Field, D. J. Young, J. Chem. Soc. Chem.Commun. 1988, 546.3 L. M. Epstein, E. S. Shubina, Coord. Chem. Rev. 2002, 231, 165.4 N. V. Belkova, E. S. Shubina, L. M. Epstein, Acc. Chem. Res. 2005, 38, 624.5 E.I. Gutsul, N.V. Belkova, M.S. Sverdlov, L.M. Epstein, E.S. Shubina, V.I. Bakhmutov,T.N. Gribanova, R.M. Minyaev, C. Bianchini, M.Peruzzini, F. Zanobini, Chem. Eur. J.2003, 9, 2219.6 N. V. Belkova, E. Collange, P. Dub, L. M. Epstein, D. A. Lemenovskii, A. Lledós, O.Maresca, F. Maseras, R. Poli, P. O. Revin, E. S. Shubina, E. V. Vorontsov. Chem. Eur. J.,2005, 11, 873.181