Electron paramagnetic resonance study of the reactions of tetrathiomolybdate with roussin salts and esters, and with some related iron nitrosyls |
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| Authors: | Anthony R Butler Christopher Glidewell Ian L Johnson John C Walton |
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| Institution: | Department of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, U.K. |
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| Abstract: | The tetrathiomolybdate ion MoS4]2− reacts in DMF solution with Roussin esters Fe2(SR)2(NO)4 (R = Me, Et, n-Pr, i-Pr, n-Bu,t-Bu, n-C5H11) to yield the paramagnetic iron nitrosyls Fe(NO)2(SR)2]− (1), Fe(NO)2(S2MoS2]− (2) and Fe(NO)(S2MOS2)2]− (3). The new complexes (2) and (3) have been characterized by EPR spectroscopy and the assignment to them of constitutions based respectively upon tetrahedral and square pyramidal iron is supported by EHMO calculations. Fe2(SPh)2(NO)4 with MoS4]2− yields only Fe(NO)2(SPh)2]−, and preformed (3) reacts with PhS− to give firstly EPR-silent species, and then Fe(NO)2(SPh)2]−. The mononitrosyl (3) can also be formed by reaction of MoS4]2− with Fe4S3(NO)7]−, Fe4S4(NO)4, or Fe2I2(NO)4. |
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