High-yield synthesis of the iron-sulfur cluster [{N(SiMe(3))(2)}{SC(NMe(2))(2)}Fe(4)S(3)](2)(mu(6)-S) {mu-N(SiMe(3))(2)}(2) (1), which reproduces the [8Fe-7S] core structure of the nitrogenase P(N)-cluster, has been achieved via two pathways: (1) Fe{N(SiMe(3))(2)}(2) + HSTip (Tip = 2,4,6-(i)Pr(3)C(6)H(2)) + tetramethylthiourea (SC(NMe(2))(2)) + elemental sulfur (S(8)); and (2) Fe(3){N(SiMe(3))(2)}(2)(mu-STip)(4) (2) + HSTip + SC(NMe(2))(2) + S(8). The thiourea and terminal amide ligands of 1 were found to be replaceable by thiolate ligands upon treatment with thiolate anions and thiols at -40 degrees C, respectively, and a series of [8Fe-7S] clusters bearing two to four thiolate ligands have been synthesized and their structures were determined by X-ray analysis. The structures of these model [8Fe-7S] clusters all closely resemble that of the reduced form of P-cluster (P(N)) having 8Fe(II) centers, while their 6Fe(II)-2Fe(III) oxidation states correspond to the oxidized form of P-cluster (P(OX)). The cyclic voltammograms of the [8Fe-7S] clusters reveal two quasi-reversible one-electron reduction processes, leading to the 8Fe(II) state that is the same as the P(N)-cluster, and the synthetic models demonstrate the redox behavior between the two major oxidation states of the native P-cluster. Replacement of the SC(NMe(2))(2) ligands in 1 with thiolate anions led to more negative reduction potentials, while a slight positive shift occurred upon replacement of the terminal amide ligands with thiolates. The clusters 1, (NEt(4))(2)[{N(SiMe(3))(2)}(SC(6)H(4)-4-Me)Fe(4)S(3)](2)(mu(6)-S){mu-N(SiMe(3))(2)}(2) (3a), and [(SBtp){SC(NMe(2))(2)}Fe(4)S(3)](2)(mu(6)-S){mu-N(SiMe(3))(2)}(2) (5; Btp = 2,6-(SiMe(3))(2)C(6)H(3)) are EPR silent at 4-100 K, and their temperature-dependent magnetic moments indicate a singlet ground state with antiferromagnetic couplings among the iron centers. The (57)Fe Mössbauer spectra of these clusters are consistent with the 6Fe(II)-2Fe(III) oxidation state, each exhibiting two doublets with an intensity ratio of ca. 1:3, which are assignable to Fe(III) and Fe(II), respectively. Comparison of the quadrupole splittings for 1, 3a, and 5 has led to the conclusion that two Fe(III) sites of the clusters are the peripheral iron atoms.

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An oxygen-encapsulated iron sulfido cluster, [(DmpS)Fe(4)S(3)O][(DmpS)Fe(4)S(3)](μ-SDmp)(2)(μ-OCPh(3)) (2; Dmp = 2,6-(mesityl)(2)C(6)H(3)), has been synthesized by the reaction of the preformed dinuclear iron thiolate/alkoxide [(Ph(3)CO)Fe](2)(μ-SDmp)(2) (1) with (1/8)S(8) and (1/4)H(2)O in toluene. In the [Fe(8)S(6)O] core, the oxygen atom bridges unsymmetrically two incomplete Fe(4)S(3) cubes, and two coordinatively unsaturated iron atoms are weakly bound to mesityl rings. Relevance of the cluster structure of 2 to the nitrogenase FeMo cofactor and its substrate binding mode is discussed.