Barbaro Pierluigi, Di Vaira Massimo, Peruzzini Maurizio, Seniori Costantini Stefano, Stoppioni Piero
ICCOM CNR, via Madonna del Piano, 10, 50019 Sesto Fiorentino, Firenze, Italy.
Chemistry. 2007;13(23):6682-90. doi: 10.1002/chem.200601846.
The reaction of [CpRu(PPh(3))(2)Cl] (1) with half an equivalent of P(4) or P(4)S(3) in the presence of AgCF(3)SO(3) as chloride scavenger affords the stable dimetal complexes [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(4))]CF(3)SO(3).3 CH(2)Cl(2) (2) and [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(apical)-P(basal)-P(4)S(3))]CF(3)SO(3).0.5 C(7)H(8) (3), in which the tetrahedral P(4) and mixed-cage P(4)S(3) molecules are respectively bound to two CpRu(PPh(3))(2) fragments through two phosphorus atoms. The coordinated cage molecules, at variance with the free ligands, readily react with an excess of water in THF under mild conditions. Among the hydrolysis products, the new, remarkably stable complexes [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(2)H(4))]CF(3)SO(3) (4) and [CpRu(PPh(3))(2)(eta(1)-PH(2)SH)]CF(3)SO(3) (8) were isolated. In the former, diphosphane, P(2)H(4), is coordinated to two CpRu(PPh(3))(2) fragments, and in the latter thiophosphinous acid, H(2)PSH, is coordinated to the metal centre through the phosphorus atom. All compounds were characterised by elemental analyses and IR and NMR spectroscopy. The crystal structures of 2, 3, 4 and 8 were determined by X-ray diffraction.
在作为氯清除剂的AgCF₃SO₃存在下，[CpRu(PPh₃)₂Cl]（1）与半当量的P₄或P₄S₃反应，得到稳定的双金属配合物[{CpRu(PPh₃)₂}₂(μ,η¹:¹-P₄)][CF₃SO₃]₂·3CH₂Cl₂（2）和[{CpRu(PPh₃)₂}₂(μ,η¹:¹-P(顶端)-P(基部)-P₄S₃)][CF₃SO₃]₂·0.5C₇H₈（3），其中四面体P₄和混合笼状P₄S₃分子分别通过两个磷原子与两个CpRu(PPh₃)₂片段相连。与游离配体不同，配位的笼状分子在温和条件下很容易与THF中过量的水反应。在水解产物中，分离出了新的、非常稳定的配合物[{CpRu(PPh₃)₂}₂(μ,η¹:¹-P₂H₄)][CF₃SO₃]₂（4）和[CpRu(PPh₃)₂(η¹-PH₂SH)]CF₃SO₃（8）。在前者中，二膦P₂H₄与两个CpRu(PPh₃)₂片段配位，在后者中，硫代亚膦酸H₂PSH通过磷原子与金属中心配位。所有化合物都通过元素分析、红外光谱和核磁共振光谱进行了表征。通过X射线衍射确定了2、3、4和8的晶体结构。
