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Acid-Base Control of Hemilabile Proton-Responsive Protecting Devices in Dimolybdenum, Thiolate-Bridged Complexes

Abstract : Dimolybdenum thiolate-bridged complexes [Mo2Cp2(μ-SMe)2(μ-SCH2CH2E)] (E = O (2) or NH (4)) with a proton-dependent protecting device have been synthesized by reaction of [Mo2Cp2(μ-SMe)2(μ-Cl)2] (1) with SCH2CH2EH. The reactivity of the resultant quadruply bridged complexes with acid was investigated in the absence and in the presence of a potential ligand (N2, MeCN, RNC). While the protonation of complexes 2 and 4 under N2 in dichloromethane produced only the oxidized derivatives instead of the desired diazenido compound, ligand binding was observed in MeCN or in the presence of RNC (R = t-Bu, Xyl). Whereas acetonitrile loss from [Mo2Cp2(μ-SMe)2(μ-SCH2CH2OH)(MeCN)2]+ (8+) prevented the isolation and characterization of this species, the t-BuNC analogue (6+) could be characterized by an X-ray crystal structure. The electrochemistry of 2 and 2+ was investigated in CH2Cl2 and in MeCN, both in the absence and in the presence of acid. While the addition of HBF4·Et2O to a dichloromethane solution of 2 only produced 2+ (and presumably H2), 8+ was the major product of the protonation in MeCN.
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https://hal.univ-brest.fr/hal-01517763
Contributor : Christine Le Roy <>
Submitted on : Wednesday, May 3, 2017 - 3:56:44 PM
Last modification on : Thursday, November 12, 2020 - 12:04:02 PM

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Alan Le Goff, David Vénec, Christine Leroy, François Y. Pétillon, Philippe Schollhammer, et al.. Acid-Base Control of Hemilabile Proton-Responsive Protecting Devices in Dimolybdenum, Thiolate-Bridged Complexes. Inorganic Chemistry, American Chemical Society, 2014, 53 (4), pp.2200 - 2210. ⟨10.1021/ic402873c⟩. ⟨hal-01517763⟩

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