Diruthenium-tin complexes from the reaction of Ph2SnH2 with Ru(CO)(5) and their reactions with bis(tri-tert-butylphosphine)platinum

作者：Adams Richard D^*; Trufan Eszter

来源：Organometallics, 2008, 27(16): 4108-4115.

DOI：10.1021/om800385w

Ph2SnH2 reacts with 2 equiv of Ru(CO)(5) to give the compound [RU(CO)(4)H](2)(mu-SnPh2) (1) in 57% yield by loss of CO from each molecule of RU(CO)(5) and by an oxidative addition of an Sn-H bond to each ruthenium atom. When compound 1 was irradiated with visible radiation, the compound Ru-2(CO)(8)(mu-SnPh2) (2) was obtained by loss of hydrogen. A mechanism involving loss of CO followed by loss of H, and readdition of CO is supported by isotopic labeling studies. Compound I reacts with Pt(PBu3t)(2) to yield the new trimetallic compound Ru-2(CO)(7)(mu-SnPh2)(mu-H)(2)(mu-PtPBu3t) (3). Compound 3 contains a Pt(CO)(PBu3t) group bridging the Ru-Ru bond and two bridging hydrido ligands. Compound 2 reacts with Pt(PBu3t)(2) to yield the two products PtRu2(CO)(8))(PBu3t)(mu-SnPh2) (4; 78% yield) and Pt2Ru2(CO)(8)(PBu3t)(2)(mu-SnPh2) (5; 15% yield) by the addition of one and two Pt(PBu3t) groups to the metal-metal bonds of 2. The first Pt(PBu3t) addition occurs at the Ru-Ru bond to form 4. The second Pt(PBu3t) addition occurs at one of the Ru-Sn bonds. Compound 4 reacts with hydrogen under irradiation with visible light to yield 3. Fenske-Hall molecular orbitals were calculated for the compounds 2-5. The molecular orbital analysis of 2 explains the nature of the addition of the Pt(PBu3t) groups to its metal-metal bonds. The molecular structures of 1-5 were determined by single-crystal X-ray diffraction analysis.

• 出版日期2008-8-25