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Electron paramagnetic resonance study of the reactions of tetrathiomolybdate with roussin salts and esters, and with some related iron nitrosyls

1987; Elsevier BV; Volume: 6; Issue: 12 Linguagem: Inglês

10.1016/s0277-5387(00)84268-0

1873-3719

Anthony R. Butler, Christopher Glidewell, Ian L. Johnson, John C. Walton,

Organometallic Compounds Synthesis and Characterization

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.