Selective syntheses of iron-imide-sulfide cubanes, including a partial representation of the Fe-S-X environment in the FeMo cofactor.
The dinuclear precursors Fe(2)(N(t)Bu)(2)Cl(2)(NH(2)(t)Bu)(2), [Fe(2)(N(t)Bu)(S)Cl(4)](2-), and Fe(2)(NH(t)Bu)(2)(S)(N{SiMe(3)}(2))(2) allowed the selective syntheses of the cubane clusters [Fe(4)(N(t)Bu)(n)(S)(4-n)Cl(4)](z) with [n, z] = [3, 1-], [2, 2-], [1, 2-]. Weak-field iron-sulfur clusters with heteroleptic, nitrogen-containing cores are of interest with respect to observed or conjectured environments in the iron-molybdenum cofactor of nitrogenase. In this context, the present iron-imide-sulfide clusters constitute a new class of compounds for study, with the Fe(4)NS(3) core of the [1, 2-] cluster affording the first synthetic representation of the corresponding heteroligated Fe(4)S(3)X subunit in the cofactor.
Chen
Xu-Dong
XD
Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
Duncan
Jeremiah S
JS
Verma
Atul K
AK
Lee
Sonny C
SC
D018360:Crystallography, X-Ray; D007094:Imides / Q000138:chemical synthesis*; D007501:Iron / Q000737:chemistry*; D008983:Molybdoferredoxin / Q000737:chemistry*; D013440:Sulfides / Q000138:chemical synthesis*
D007094:Imides; D008983:Molybdoferredoxin; D013440:Sulfides; D007501:Iron