31P NMR Studies on Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum Cluster Compounds. X-ray Structures of [Mo3OS3(DTP)4(CH3CN)] and [Mo3OS3(OAc)(DTP)2(Py)2(OC2H5)]

Yao, Yuangen; Akashi, Haruo; Sakane, Genta; Shibahara, Takashi; Ohtaki, Hitoshi

diethyldithiophosphoric acid, molybdenum
S/O-bridged incomplete cubane-type Mo cluster compds. [Mo3OnS4-n(DTP)4(L)] (n = 0-3; DTP = di-Et dithiophosphate, L = monodentate ligand), and their ligand substitution derivs. were prepd. by the reaction of the corresponding aqua ions with the ligand DTP.  The crystallog. results obtained are as follows.  [Mo3OS3(DTP)4(MeCN)]: triclinic, space group P-1, a 14.134(13), b 16.413(16), c 10.654(9) angstrom, a 98.08(10), b 112.23(6), g 77.03(9)degree, Z = 2, no. of unique data (
Fo
 > 6σ
Fo
) = 4810, R = 4.79%.  [Mo3OS3(OAc)(DTP)2(Py)2(OEt)]: triclinic, space group P-1, a 13.985(7), b 14.359(7), c 12.012(4) angstrom, a 96.01(3), b 104.37(3), g 114.20(3)degree, Z = 2, no. of unique data (
Fo
 > 3σ
Fo
) = 4944, R = 4.62%.  Of four DTP ligands in [Mo3OS3(DTP)4(MeCN)], three are terminal and one is bridging.  Both DTP ligands in [Mo3OS3(OAc)(DTP)2(Py)2(OEt)] are terminal, and an acetato ligand is bridging.  31P NMR spectra of these cluster compds. were measured in a soln. of o-dichlorobenzene and MeCN.  The 31P NMR spectra of these cluster compds. presented much information about the structure, interaction between the ligands and the cluster core, solvent effect, lability of the ligands, and isomerization of this cluster compd. series.  The assignment of the chem. shifts to each distinct ligand under different circumstances was successfully accomplished.  The site of the loosely-coordinated solvent ligand L was kinetically active and informative to the assignments of the spectra.  The symmetry and chem. properties of the central trinuclear cluster core Mo3OnS4-n (n = 0-3) were also well reflected in their spectral appearance.

Inorganic Chemistry

American Chemical Society

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