Cubane-Type Molybdenum-Zinc or -Cadmium Mixed-Metal Clusters with Diethyldithiophosphate or Nitrilotriacetate Ligands

Sakane, Genta; Kawasaki, Hideki; Oomori, Takashi; Yamasaki, Mikio; Adachi, Hirohiko; Shibahara, Takashi

molybdenum zinc cadmium mixed metal cluster thiophosphate nitrilotriacetate prepn; crystal structure molybdenum zinc cadmium sulfido; electronic structure molybdenum zinc cadmium mixed cluster thiophosphate nitrilotriacetate
The reactions of S-bridged clusters, [Mo3(μ3-S)(μ-S)3(μ-dtp)(dtp)3(MeCN)] (1; dtp = diethyldithiophosphate) in MeCN or [Mo3(μ3-S)(μ-S)3(Hnta)3]2- (2; H3nta = nitrilotriacetic acid) in pure H2O, with Zn or Cd metal gave three novel Mo-Zn or Mo-Cd mixed-metal clusters, [Zn{(μ3-S)4Mo3(μ-dtp)(dtp)3 (MeCN)}2] (3), [Cd{(μ3-S)4Mo3(μ-dtp)(dtp)3(MeCN)}2] (4), and [Cd{(μ3-S)4Mo3(Hnta)3}2]4- (5), resp.  The x-ray crystal structures of (1).H2O(1'), 3, 4, and [Co(H2O)6]2(5).22H2O (5') were detd., and the existence of the sandwich cubane-type cores Mo3S4MS4Mo38+ cores (M = Zn, Cd) in 3, 4, and 5' verified.  By the change of the ligands, the peak positions at the longest wavelength in the electronic spectra are distinctly different from each other between 4 (856 nm) and 6 (1235 nm).  The electronic structures of 3, 4, and 5 were calcd. by Discrete Variational (DV)-Xα method.

Journal of Cluster Science

Kluwer Academic Publishers

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