Os3(CO)10(NCMe)2 reacts with PhAu(PPh3), 1  by the elimination of the two labile NCMe ligands and oxidative addition of the Au � C bond of 1  to yield the unsaturated 46 electron triosmium complex Os3(CO)10(�-Au(PPh3)](�-?1-Ph), 2  which contains a bridging ?1-phenyl ligand and a bridging Au(PPh3) group across the same Os � Os bond. The phenyl ring undergoes hindered rotation about the Os � Os bond in 2  . The rotational barrier was determined by VT NMR measurements and the mechanism was analyzed by DFT methods. When heated, 1  lost CO and was transformed into Os3(CO)10(�-Au(PPh3)](�3-?2-C6H4)(�-H), 3  by CH activation and transfer of one of the phenyl hydrogen atoms to the cluster with formation of a triply bridging benzyne C6H4 ligand. Os3(CO)10(NCMe)2 oxidatively adds NpAu(PPh3), Np = naphthyl to yield the complex Os3(CO)10(�-Au(PPh3)](�-2-Np), 4  which exists as two isomers in the solid state. One isomer is unsaturated and contains a ?1-bridging 2-naphthyl ligand analogous to that of the phenyl ligand in 2  . The second isomer is electronically saturated and contains a bridging 2-naphthyl ligand having a bridging ?2-coordination that serves as a 3-electron donor. When heated, compound 4  lost CO and was converted into the naphthyne compound Os3(CO)10(�3-1,2-?2-C10H6)(�-AuPPh3)(�-H). Re2(CO)8[�-C(H)C(H)C4H9](�-H) reacted with 1  to yield the unsaturated dirhenium compound Re2(CO)8(�-Au(PPh3)](�-?1-Ph), 5  that contains a bridging ?1-phenyl ligand and a bridging Au(PPh3) group across the Re � Re bond. The reaction of the anion [Ir4(CO)11(Ph-)]- with [Cu(NCMe)4]BF4 yielded the complex Ir4(CO)11[�-Cu(NCMe)](�-?1-Ph) that contains a semibridging ?1-phenyl ligand from Ir to Cu. The reaction of [Ir4(CO)11(Ph-)]- with Ag[NO3] yielded the complex [Ir4(CO)11]2(�4-Ag)(�-Ag)(�3-Ph)(�-Ph) that contains one edge-bridging and one triply-bridging phenyl ligand.

Coordination chemistry between two metal atoms: The unusual coordination chemistry of bridging aryl ligands

246th National Meeting (2013)

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