Synthesis, structure, and 31P NMR of sulfur/oxygen-bridged incomplete cubane-type molybdenum and tungsten clusters with triphenylphosphine ligands

Sasaki, Mari; Sakane, Genta; Ouchi, Tadashi; Shibahara, Takashi

crystal structure molybdenum tungsten incomplete cubane; molybdenum incomplete cubane phosphine cluster prepn; tungsten incomplete cubane phosphine cluster prepn; sulfur tungsten molybdenum incomplete cubane prepn; oxide sulfido molybdenum incomplete cubane prep; phosphine tungsten molybdenum incomplete cubane prepn
S/O-bridged incomplete cubane-type PPh3 Mo-and W-clusters [Mo3S4Cl4(H2O)2(PPh3)3].3THF (1A), [Mo3S4Cl4(H2O)2(PPh3)3].2THF (2A), [Mo3OS3Cl4(H2O)2(PPh3)3].2THF (1B), and [W3S4Cl4(H2O)2(PPh3)3].2THF (1C) were prepd. from the corresponding aqua clusters and PPh3 in THF/MeOH.  On recrystn. from THF, procedures with and without addn. of hexane to the soln. gave 1A and 2A, resp., while the procedures gave no effect on the formation of 1B and 1C.  Crystallog. results obtained are as follows: 1A: monoclinic, space group P21/n, a 17.141(4), b 22.579(5), c 19.069(4) angstrom, b 96.18(2)degree, Z = 4, R(Rw) = 0.078(0.102); 1C: monoclinic, space group P21/c, a 12.635(1), b 20.216(4), c 27.815(3) angstrom, b 96.16(1)degree, V = 7062(2) angstrom cubed, Z = 4, R(Rw) = 0.071(0.083).  If the Ph groups are ignored, the mol. [Mo3S4Cl4(H2O)2(PPh3)3] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane detd. by the metal atoms, while the mol. in 1A does not have the symmetry.  The W compd. 1C is isomorphous with the Mo compd. 2A.  31P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands.

Journal of Cluster Science

Kluwer Academic Publishers

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