54955-47-4Relevant articles and documents
Photochemistry and electronic structure of the (η5-C5H5)2MoS2 complex
Bruce, Alice E.,Bruce, Mitchell R. M.,Sclafani, Anthony,Tyler, David R.
, p. 1610 - 1614 (2008/10/08)
The photochemistry of the Cp2MoS2 complex was studied in order to determine if d-d excited states gave different photochemistry than the S → Mo charge-transfer excited states. The various excited states were identified with the aid of a self-consistent field-Xα-scattered-wave molecular orbital calculation. No wavelength dependent photochemistry was found as irradiation of the Cp2MoS2 complex in inert solvents at all selected wavelengths led to Cp2MoS4. The mechanism of Cp2MoS4 formation was studied. Two pathways seemed likely: photochemical extrusion of either S2 or S22-. The formation of Cp2MoS4 does not necessarily imply the extrusion of S2 rather than S22- because the latter species can disproportionate: 2S22- → S2 + 2S2-. In order to differentiate between homolytic and heterolytic Mo-S bond cleavage pathways, the Cp2MoS2 complex was irradiated in CDCl3. The products in this solvent are Cp2MoCl2 and Cp2MoS4, at all wavelengths. Other unidentified minor products also formed in the photochemical reactions of the Cp2MoS2. Since the reaction of molybdenocene with CHCl3 produces Cp2MoCl2 and because attempts to trap Cp2Mo2+ failed, it is proposed that homolytic extrusion of S2 follows irradiation of the Cp2MoS2 complex. Reasons for the wavelength independent photochemistry and for the homolytic extrusion of S2, upon irradiation in either the 14a1 → 9b1 d-d band (490 nm) or the 6a2 → 9b1 S → Mo charge-transfer (420 nm) band, are discussed.
