The reaction of Os 3 (CO) 12 with Ph 3 SnH yielded the bimetallic Os−Sn cluster complexes Os 3 (CO) 11 (SnPh 3 )(μ-H) ( 16 ) and Os 3 (CO) 9 (μ-SnPh 2 ) 3 ( 17 ) in 20 and 21% yields, respectively. Compound 16 consists of an Os 3 triangle with a terminal SnPh 3 group on one of the Os atoms and a bridging hydrido ligand across one of the Os−Os bonds. Compound 17 consists of a central Os 3 triangle with SnPh 2 groups bridging each of the three Os−Os bonds. Pt(PBu t 3 ) 2 reacts with compound 17 to afford Os 3 (CO) 9 [Pt(PBu t 3 )](μ-SnPh 2 ) 3 ( 18 ), a Pt(PBu t 3 ) adduct of 17, in 29% yield by adding a Pt(PBu t 3 ) group across one of the Os−Sn bonds. The osmium and tin atoms lie in a plane, while the Pt(PBu t 3 ) group is displaced slightly out of that plane. Pt(PPh 3 ) 4 reacts with 17 to give the cluster complex Os 3 (CO) 9 [Pt(Ph)(PPh 3 ) 2 ](μ-SnPh 2 ) 2 (μ 3 -SnPh) ( 19 ) in 21% yield by insertion of a Pt(PPh 3 ) 2 into one of the Sn−C bonds to one of the phenyl groups. The osmium and tin atoms are coplanar, and there is a Pt(Ph)(PPh 3 ) 2 group terminally bonded to one of the tin atoms. The platinum atom of the Pt(Ph)(PPh 3 ) 2 group has a square-planar geometry with the two PPh 3 ligands in cis coordination sites. All new products were characterized crystallographically by single-crystal X-ray diffraction techniques.
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Adams et al. (2006) studied this question.
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