H(+)/AuPPh(3)(+) Exchange for the Hydride Complexes CpMoH(CO)(2)(L) (L = PMe(3), PPh(3), CO). Formation and Structure of [Cp(CO)(2)(PMe(3))Mo(AuPPh(3))(2)](+)[BF(4)](-).
The reaction of CpMoH(CO)(2)L with AuPPh(3)(+)BF(4)(-) in THF at -40 degrees C proceeds directly to the MoAu(2) cluster compounds [CpMo(CO)(2)L(AuPPh(3))(2)](+)BF(4)(-) (L = PMe(3) (1), PPh(3) (2)) with release of protons. A 1:1 reaction leaves 50% of the starting hydride unreacted. At lower temperature, however, the formation of a [CpMo(CO)(2)(PMe(3))(&mgr;-H)(AuPPh(3))](+) intermediate is observed. This compound evolves to the cation of 1 and CpMoH(CO)(2)(PMe(3)) upon warming and is deprotonated by 2,6-lutidine to afford CpMo(CO)(2)(PMe(3))(AuPPh(3)). The X-ray structure of 1 can be described as a four-legged piano stool with the PMe(3) and the "eta(2)-(AuPPh(3))(2)" ligands occupying relative trans positions. [Cp(CO)(2)(PMe(3))Mo(AuPPh(3))(2)](+)[BF(4)](-) (M(r) = 1298.41): monoclinic, space group P2(1)/n, a = 18.1457(13) Å, b = 9.7811(7) Å, c = 26.096(2) Å, beta = 105.086(5) degrees, V = 4472.0(5) Å(3), Z = 4. The reaction of CpMoH(CO)(2)(PMe(3)) with 3 equiv of AuPPh(3)(+) affords a MoAu(3) cluster, [CpMo(CO)(2)(PMe(3))(AuPPh(3))(3)](2+) (3), in good yields under kinetically controlled conditions. Under thermodynamically controlled conditions, 3 dissociates extensively into 1 and free AuPPh(3)(+). It is proposed that the hydride ligand helps build higher nuclearity Mo-Au clusters. The difference in reaction pathways for the interaction of AuPPh(3)(+) with CpMoH(CO)(2)L when L = PR(3) or CO and for the interaction of CpMoH(CO)(2)(PMe(3)) with E(+) when E = H, Ph(3)C or AuPPh(3) is discussed. The lower acidity and greater aurophilicity of the [CpMo(CO)(2)L(&mgr;-H)(AuPPh(3))](+) intermediate when L = PMe(3) favor attack by AuPPh(3)(+) before deprotonation.
Galassi
Rossana
R
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742.
Poli
Rinaldo
R
Quadrelli
E. Alessandra
EA
Fettinger
James C.
JC