Investigation on the protonation of a trisubstituted [Fe(2)(CO)(3)(PPh(3))(kappa(2)-phen)(mu-pdt)] complex: rotated versus unrotated intermediate pathways.

Pierre-Yves Orain (1) , Jean-François Capon (1) , Frederic Gloaguen (1) , François Y. Pétillon (1) , Philippe P. Schollhammer (1) , Jean Talarmin (1) , Giuseppe Zampella , Luca de Gioia , Thierry Roisnel (2)

1 CEMCA - Chimie, Electrochimie Moléculaires et Chimie Analytique
2 ISCR - Institut des Sciences Chimiques de Rennes

The substitution of PPh(3) for a carbonyl group at the {Fe(CO)(3)} moiety in [Fe(2)(CO)(4)(kappa(2)-phen)(mu-pdt)] results in the formation of the trisubstituted complex [Fe(2)(CO)(3)(PPh(3))(kappa(2)-phen)(mu-pdt)] (2). Unlike its tetracarbonyl precursor, the protonation of 2 at low temperature does not afford any apparent transient terminal hydride species. Hydride formation for [Fe(2)(CO)(3)(L)(kappa(2)-phen)(mu-pdt)] (L = PPh(3), CO) species is also studied by density functional theory calculations, which show that activation barriers to give terminal and bridging hydrides can be remarkably close for this class of organometallic compounds.

Mots clés: Coordination Complexes/chemistry; Crystallography; X-Ray; Models; Molecular; Molecular Conformation; Protons; Rotation; Stereoisomerism

Domaines: Chimie inorganique; Chimie de coordination

Pierre-Yves Orain, Jean-François Capon, Frederic Gloaguen, François Y. Pétillon, Philippe P. Schollhammer, et al.. Investigation on the protonation of a trisubstituted [Fe(2)(CO)(3)(PPh(3))(kappa(2)-phen)(mu-pdt)] complex: rotated versus unrotated intermediate pathways.. Inorganic Chemistry, 2010, 49 (11), pp.5003-8. ⟨10.1021/ic100108h⟩. ⟨hal-00737677⟩