Synthesis and structures of the cuboidal iron-sulfur-nitrosyl-phosphine clusters [Fe 4S 3(NO) 4(PR 3) 3] 0,1+ (R = Et, Pr i, C 6H 11)

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A series of cuboidal iron-sulfur clusters [Fe 4S 3(NO) 4(PR 3) 3] 0,1+ (R = Et, Pr i, Cy) were synthesized by two routes: reductive desulfurization of [Fe 4S 4(NO) 4] by tertiary phosphines, and substitution of triphenylphosphine in [Fe 44S 3(NO) 4(PPh 3) 3] by a more basic phosphine. The structures of 3[Fe 4S 3(NO) 4(PEt 3) 3] · 0.5Et 2O, [Fe 4S 3(NO) 4(PEt 3) 3] [Fe 4S 3(NO) 7] and partially substituted [Fe 4S 3(NO) 4(PPh 3) 2 − (PPr i 3)] have been determined by X-ray diffraction in order to define the cuboidal Fe 4S 3 core, previously known only in Roussin's black anion and its reduced form, [Fe 4S 3(NO) 77] 1−,2−, and as a part of the iron-molybdenum cofactor of nitrogenase.