Syntheses, Characterization and X-ray Crystal Structures of Diiron Ethanedithiolate Complexes Fe_2(S

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Two new diiron ethanedithiolate complexes Fe2(S2C2H4)(CO)5 (2-Ph2PC6H4NH2) (1) and Fe2(S2C2H4)(CO)5 (2-Ph2PC6H4CH2NH2) (2) as active site models of [FeFe] hydrogenases have been prepared by the treatment of (μ-SCH2CH2 S-μ)Fe2(CO)6 with 2-Ph2PC6H4NH2 or 2-Ph2PC6H4CH2NH2 in the presence of the decarbonylating agent Me3NO·2H2O. As new complexes, both 1 and 2 were fully characterized by elemental analysis, IR and 1H ( 13C, 31P) NMR spectroscopies. In addition, the molecular structure of complex 1 was established by X-ray crystallography. The crystal of Fe2(S2C2H4 )(CO) 5(2-Ph2PC6H4NH2) (1) crystallizes in orthorhombic, spacegroup Pna21 with a = 20.9461(17), b = 13.7615(11), c = 9.3133(7), V = 2684.6(4)3 , Z = 4, C25H20Fe2NO5PS2, Mr = 621.21, Dc = 1.537 g/cm 3 , F(000) = 1264. The final R = 0.0197 and wR = 0.0495 for 4605 observed reflections with I > 2σ(I) and R = 0.0206 and wR = 0.0501 for all data. Two new diiron ethanedithiolate complexes Fe2 (S2C2H4) (CO) 5 (2-Ph2PC6H4NH2) (1) and Fe2 (S2C2H4) (CO) 5 (2-Ph2PC6H4CH2NH2) (2) as active site models of [FeFe] by the treatment of (μ-SCH2CH2S-μ) Fe2 (CO) 6 with 2-Ph2PC6H4NH2 or 2-Ph2PC6H4CH2NH2 in the presence of the decarbonylating agent Me3NO · 2H2O. As new complexes, both 1 and 2 were fully characterized by elemental analysis , IR and 1H (13C, 31P) NMR spectroscopies. In addition, the molecular structure of complex 1 was established by X-ray crystallography. The crystal of Fe2 (S2C2H4) (CO) 5 (2-Ph2PC6H4NH2) (1) crystallizes in orthorhombic space group Pna21 with a = 20.9461 (17) b = 13.7615 (11) c = 9.3133 (7)  V = 2684.6 (4) 3 Z = 4 C25H20Fe2NO5PS2 Mr = 621.21 Dc = 1.537 g / cm 3, F (000) = 1264. The final R = 0.0197 and wR = 0.0495 for 4605 observed reflections with I> 2σ (I) and R = 0.0206 and wR = 0.0501 for all data.
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