Reactions of 1,8-bis(diphenylphosphino)naphthalene with Os3(CO)12: C–H and C–P bond cleavage reactions

Reactions of Os3(CO)12 with 1,8-bis(diphenylphosphino)naphthalene (dppn) are described. Crystallographically characterised complexes isolated from a reaction carried out in refluxing toluene are Os3(μ-H)2{μ-PPh2(nap)PPh(C6H4)}2(CO)6 (1), Os3(μ-H){μ3-PPh2(nap)PPh(C6H4)}(CO)8 (2) and Os2(μ-PPh2){μ-PPh2(nap)}(CO)5 (3) (nap=1,8-C10H6), while at r.t. in the presence of ONMe3, only Os3(CO)11{PPh2(1-C10H7)} (4) was isolated. While 1 and 2 contain ligands formed by metallation of a Ph group of dppn, as found also in complexes obtained from dppn and Ru3(CO)12, ligands in 3 and 4 are formed by cleavage of a P-nap bond, not found in the Ru series.Four complexes isolated from reactions between Os3(CO)12 and 1,8-bis(diphenylphosphino)naphthalene (dppn) contain ligands formed by cleavage of C–H and C–P bonds in the dppn, with P-phenyl groups attached by η1 or η1: η2 modes. Also formed is a complex containing PPh2(C10H7-1).