Université Européenne de Bretagne, France.
Inorg Chem. 2010 Jun 7;49(11):5003-8. doi: 10.1021/ic100108h.
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.
三膦取代 [Fe(2)(CO)(4)(κ(2)-phen)(μ-pdt)] 中 CO 基团生成三取代配合物 [Fe(2)(CO)(3)(PPh(3))(κ(2)-phen)(μ-pdt)]（2）。与四羰基前体不同，2 在低温下质子化时不会生成任何明显的瞬态末端氢化物物种。通过密度泛函理论计算研究了[Fe(2)(CO)(3)(L)(κ(2)-phen)(μ-pdt)]（L = PPh(3)，CO）物种的氢化物形成，结果表明该类有机金属化合物生成末端和桥接氢化物的活化势垒可以非常接近。
