Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain.
Inorg Chem. 2009 Oct 19;48(20):9767-78. doi: 10.1021/ic901340w.
The title complex reacts with Au(PR(3)) cations (PF(6)(-) salts, R = p-tol, Me) in dichloromethane solutions to give first the corresponding agostic-like products [AuMo(2)Cp(2)(mu-PEt(2))(mu(3)-PEt(2))(CO)(2)(PR(3))]PF(6), which then partially rearrange to reach an equilibrium with the hydride-like isomers [AuMo(2)Cp(2)(mu-PEt(2))(2)(CO)(2)(PR(3))]PF(6), the latter being characterized through an X-ray study (R = p-tol, Mo-Mo = 2.8244(2) A). These unsaturated complexes react smoothly with CO (1 atm) to give the corresponding electron-precise derivatives AuMo(2)Cp(2)(mu-PEt(2))(2)(CO)(3)(PR(3)) (Mo-Mo = 3.0438(6) A when R = Me), this implying the rearrangement of the mu(3)-PEt(2) ligand to a more common mu(2)-coordination mode. Density functional theory (DFT) calculations on the dimolybdenum complexes [Mo(2)Cp(2)(mu-PR(2))(2)(CO)(2)] (R = Cy, Et) reveal the presence of a framework M-P bonding orbital high in energy and with the right shape to act as a donor to H(+) and Au(PR(3)) cations, thus explaining the formation of agostic and agostic-like products respectively in these reactions. The unusually high energy of this donor orbital can be related to the close approach of the metal centers in these unsaturated molecules. The carbyne complex [Mo(2)Cp(2)(mu-COMe)(mu-PCy(2))(CO)(2)] reacts with Au{P(p-tol)(3)} to give the tricarbonyl AuMo(2)Cp(2)(mu-COMe)(mu-PCy(2))(CO)(3){P(p-tol)(3)} (Mo-Mo = 2.986(1) A), a process most likely initiated by the binding of the gold cation to one of the Mo-P bonds in the carbyne complex.
标题配合物与Au(PR(3))阳离子（PF(6)(-)盐，R = p-tol，Me）在二氯甲烷溶液中反应，首先得到相应的似桥连产物[AuMo(2)Cp(2)(mu-PEt(2))(mu(3)-PEt(2))(CO)(2)(PR(3))]PF(6)，然后部分重排以达到与氢化物类似物[AuMo(2)Cp(2)(mu-PEt(2))(2)(CO)(2)(PR(3))]PF(6)的平衡，后者通过 X 射线研究得到表征（R = p-tol，Mo-Mo = 2.8244(2)A）。这些不饱和配合物与 CO（1atm）反应平稳，得到相应的电子精确衍生物AuMo(2)Cp(2)(mu-PEt(2))(2)(CO)(3)(PR(3))（当 R = Me 时，Mo-Mo = 3.0438(6)A），这意味着 mu(3)-PEt(2)配体的重排到更常见的 mu(2)-配位模式。二钼配合物[Mo(2)Cp(2)(mu-PR(2))(2)(CO)(2)]（R = Cy，Et）的密度泛函理论（DFT）计算表明，存在一个高能量的框架 M-P 成键轨道，形状合适，可以作为 H(+)和Au(PR(3))阳离子的供体，因此分别解释了这些反应中桥连和桥连类似物的形成。这个供体轨道的能量异常高，可能与这些不饱和分子中金属中心的紧密接近有关。炔烃配合物[Mo(2)Cp(2)(mu-COMe)(mu-PCy(2))(CO)(2)]与Au{P(p-tol)(3)}反应得到三羰基AuMo(2)Cp(2)(mu-COMe)(mu-PCy(2))(CO)(3){P(p-tol)(3)}（Mo-Mo = 2.986(1)A），这个过程很可能是由金阳离子与炔烃配合物中的一个 Mo-P 键结合引发的。
