Adduct of Acetylene at Sulfur in an Oxygen- and Sulfur-Bridged Open Cubane Cluster Complex of Tungsten

Maeyama, Masataka; Sakane, Genta; Pierattelli, Roberta; Bertini, Ivano; Shibahara, Takashi

acetylene addn sulfide tungsten oxo cubane; tungsten oxo ethenylthiolato sulfide cubane prepn structure; crystal structure tungsten oxo ethenylthiolato sulfide cubane
Formation of a single C-S bond is described.  The reaction of incomplete cubane-type S and O-bridged isothiocyanato W cluster [W3(μ3-S)(μ-O)(μ-S)2(NCS)9]5- (7) with acetylene affords [W3(μ3-S)(μ-O)(μ-S)(μ-SCH:CH2)(NCS)9]4- (8).  The cluster 8 was isolated as K0.5(Hpy)3.5[W3(μ3-S)(μ-O)(μ-S)(μ-SCH:CH2)(NCS)9] (8'), whose structure was characterized by x-ray crystallog., electronic spectra, and 1H and 13C NMR spectroscopy.  Crystal data of 8': triclinic system, space group P.hivin.1, a 14.465(5), b 17.353(3), c 10.202(2) Å, α 90.98(1), β 108.59(2), γ 98.13(2)゜, Z = 2, dc = 2.096 g cm-3, Dm = 2.08 g cm-3, R (Rw) = 3.6 (5.5)% for 8786 reflections (I > 1.50 s(I)).  The C-C distance is 1.27(1) Å and is almost equidistant between ethylene (1.339 Å) and acetylene (1.203 Å).  The electronic spectrum of 8' in 1.0M HCl contg. 1.5M KSCN has a characteristic broad peak in the near-IR region [λmax, nm (e, M-1 cm-1): 840(650), 575(1450)].  1H NMR and HH correlation spectroscopy (COSY) of 8' in CD3CN support the results of the x-ray structural anal.  The 1H NMR spectrum shows three signals at 2.42 (1H, dd), 4.84 (1H, d, J = 8.8 Hz), and 4.89 (1H, d, J = 16.2 Hz) ppm due to the m-SCH:CH2 moiety of 8'.  The correlation spectrum shows spin couplings of the signal at 2.42 ppm with the signals at 4.84 and 4.89 ppm.  The mechanism of the formation of 8 probably proceeds through an intermediate with acetylene bridging two of the S atoms.

Inorganic Chemistry

アメリカ化学会

40

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