Reactions of [Os-3(CO)(10)(NCMe)(2)] 1 with norbornene (bicyclo[2.2.1]hept-
2-ene, nbe) led to two isomeric triosmium clusters [Os-3(mu-H)(CO)(10)(mu-e
ta(1):eta(2)-C7H9)] 2 and 3 and also the dihydride species [Os-3(mu-H)(2)(C
O)(9)(mu(3)-eta(1):eta(2):eta(1)-C7H8)] 4. The molecular structure of compo
und 4 established by single crystal X-ray analysis shows norbornene-metal i
nteractions similar to the proposed adsorption mode of norbornene found on
the Pt(111) surface. The two isomers 2 and 3 exhibit an intermediate bondin
g mode between the solely pi bound ligand and the di-sigma,pi bonding mode
exhibited by cluster 4. These isomers differ in the orientation of the C7H8
moiety with respect to the triosmium triangle. Both 2 and 3 may exist in o
ther isomeric forms which differ in the location of the hydride ligand. Com
pound 2 converts into 3 which on heating undergoes C-H bond cleavage to pro
duce 4.