Synthesis and structures of the cuboidal iron-sulfur-nitrosyl-phosphine clusters [Fe4S3(NO)4(PR3)3] (R = Et, Pr, C6H11) |
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| Authors: | Christopher Goh and R.H. Holm |
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| Affiliation: | Department of Chemistry, Harvard University, Cambridge, MA 02138, USA |
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| Abstract: | A series of cuboidal iron-sulfur clusters [Fe4S3(NO)4(PR3)3]0,1+ (R = Et, Pri, Cy) were synthesized by two routes: reductive desulfurization of [Fe4S4(NO)4] by tertiary phosphines, and substitution of triphenylphosphine in [Fe44S3(NO)4(PPh3)3] by a more basic phosphine. The structures of 3[Fe4S3(NO)4(PEt3)3] · 0.5Et2O, [Fe4S3(NO)4(PEt3)3] [Fe4S3(NO)7] and partially substituted [Fe4S3(NO)4(PPh3)2− (PPri3)] have been determined by X-ray diffraction in order to define the cuboidal Fe4S3 core, previously known only in Roussin's black anion and its reduced form, [Fe4S3(NO)77]1−,2−, and as a part of the iron-molybdenum cofactor of nitrogenase. |
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| Keywords: | Crystal structures Iron complexes Sulfur complexes Nitrosyl complexes Cuboidal cluster complexes |
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