Barbaro Pierluigi, Di Vaira Massimo, Peruzzini Maurizio, Seniori Costantini Stefano, Stoppioni Piero
ICCOM CNR, via Madonna del Piano, 10, 50019, Sesto Fiorentino, Firenze, Italy.
Inorg Chem. 2009 Feb 2;48(3):1091-6. doi: 10.1021/ic801859z.
The bimetallic compound [{CpRu(PPh(3))(2)}(2)(mu,eta(1:1)-P(4))]CF(3)SO(3), in which the tetrahedral P(4) is bound to two CpRu(PPh(3))(2) fragments, slowly reacts under mild conditions with a moderate excess of water (1:20) to yield a mixture of compounds. Among the hydrolysis products, the new, remarkably stable complexes {CpRu(PPh(3))}{CpRu(PPh(3))(2)}{mu(1,4:3),eta(2:1)-P(OH)(2)PHPHPH(OH)}(2) (2) and {CpRu(PPh(3))(2)}{CpRu(PPh(3)){P(OH)(3))}(mu,eta(1:1)-P(2)H(4))(2) (3) have been isolated. In the former, the previously unknown 1,1,4-tris(hydroxy)tetraphosphane molecule, P(OH)(2)PHPHPH(OH), is 1,4- and, respectively, 3-coordinated to the CpRu(PPh(3)) and the CpRu(PPh(3))(2) moieties; in the latter, the diphosphane P(2)H(4) is stabilized through coordination to two different metal fragments. All of the compounds were characterized by elemental analyses and IR and NMR spectroscopy. The crystal structure of 2 was determined by X-ray analysis. The formation of the hydroxytetraphosphane, containing the tetraphosphorus entity, provides a clue to the hydrolytic activation of the P(4) molecule.
双金属化合物[{CpRu(PPh(3))(2)}(2)(μ,η(1:1)-P(4))]CF(3)SO(3)中，四面体P(4)与两个CpRu(PPh(3))(2)片段相连，在温和条件下，它与适度过量的水（1:20）缓慢反应，生成化合物混合物。在水解产物中，已分离出新型且稳定性极高的配合物{CpRu(PPh(3))}{CpRu(PPh(3))(2)}{μ(1,4:3),η(2:1)-P(OH)(2)PHPHPH(OH)}(2)（2）和{CpRu(PPh(3))(2)}{CpRu(PPh(3)){P(OH)(3))}(μ,η(1:1)-P(2)H(4))(2)（3）。在前者中，此前未知的1,1,4-三（羟基）四膦分子P(OH)(2)PHPHPH(OH)分别与CpRu(PPh(3))和CpRu(PPh(3))(2)部分形成1,4-配位和3-配位；在后者中，双膦P(2)H(4)通过与两个不同的金属片段配位而稳定。所有化合物均通过元素分析、红外光谱和核磁共振光谱进行了表征。通过X射线分析确定了2的晶体结构。含有四磷实体的羟基四膦的形成，为P(4)分子的水解活化提供了线索。
