ABSTRACT
The first triethylphosphine-stabilized Pt-Au cluster compounds, [Pt(AuPEt(3))(10)](2+) (2) and [Pt(AuPEt(3))(9)](3+) (3), were prepared by the direct reaction of Pt(PEt(3))(3) with AuPEt(3)NO(3) under a dihydrogen atmosphere. Cluster 2 is the highest-nuclearity homoleptic Pt(AuPR(3))(n)() cluster yet prepared. The reactivity and structures of these clusters are in agreement with the well-established electron-counting arguments. The 18-electron cluster 2 was converted into the 16-electron cluster 3 by oxidation with 2 equiv of ferricinium ion [Fe(eta(5)-C(5)H(5))(2)](+). Cluster 3 was converted into 2 by reduction with H(2) in the presence of [AuPEt(3)](+). Cluster 3 was also observed to cleanly add the 2-electron donors CO and PEt(3) to form the 18-electron clusters [(CO)Pt(AuPEt(3))(9)](3+) (4) and [(PEt(3))Pt(AuPEt(3))(9)](3+) (5), respectively. Single-crystal X-ray diffraction results show that 3 has a flattened, toroidal structure in which the PtAu(9) framework has a Pt-centered, tricapped trigonal prismatic geometry. Crystal data for [Pt(AuPEt(3))(9)](NO(3))(3) is as follows: hexagonal P6(3)/m, a = 15.134(5) Å, c = 23.48(1) Å, V = 4657 Å(3), Z = 2, residuals R = 0.056, and R(w)() = 0.053 for 1489 observed reflections and 81 variables, Mo Kalpha radiation. Compound 3 was found to reversibly add H(2) in solution to form the dihydride cluster [(H)(2)Pt(AuPEt(3))(9)](3+) (6). The equilibrium constant for this addition reaction is 1.1 x 10(3) M(-)(1) (CD(2)Cl(2) solution, 25 degrees C), slightly smaller than that for [Pt(AuPPh(3))(8)](2+). The rate of the addition is also slower than that with [Pt(AuPPh(3))(8)](2+). Cluster 3 is an excellent homogeneous catalyst for H(2)-D(2) equilibration giving a turnover rate for HD production of 0.13 s(-)(1) (nitrobenzene solvent, 30 degrees C, 1 atm). The PEt(3)-containing clusters give similar rates and follow the same general trends previously observed with PPh(3)-ligated clusters. The chemistry of these new clusters is explained by consideration of the steric and electronic properties of the PEt(3) ligand. These new compounds will be useful as models for hydrogen activation by Pt-Au clusters and as precursors for supported Pt-Au catalysts.
