Synthesis and Crystal Structures of Diiron Dithiolate Complexes Containing Diphosphine Ligands

• Published in: Journal of cluster science Vol. 25; no. 2; pp. 495 - 503
• Main Authors: Liu, Xu-Feng, Gao, Hao-Qi
• Format: Journal Article
• Language: English
• Published: Boston Springer US 01.03.2014; Springer Nature B.V
• Subjects: Atomic structure; Catalysis; Chemical analysis; Chemistry; Chemistry and Materials Science; Clusters; Coordination; Crystal structure; Crystallography; Diffraction; Hydrogenase; Infrared radiation; Inorganic Chemistry; Ligands; Molecular structure; Nanochemistry; Neutrons; NMR; Nuclear magnetic resonance; Original Paper; Physical Chemistry; Room temperature; Single crystals; Synthesis; X-rays; Carbonyl substitution; Synthesis; Diiron dithiolate; Diphosphine ligand; Crystal structure
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1007/s10876-013-0627-7

As the active site model of [FeFe]-hydrogenases, complexes [( μ -PDT)Fe 2 (CO) 5 ] 2 (dppb) (PDT = SCH 2 CH 2 CH 2 S, dppb = Ph 2 PCH 2 CH 2 CH 2 CH 2 PPh 2 ) ( 1 ) and [( μ -SCH 2 ) 2 NCH 2 CO 2 Me]Fe 2 (CO) 5 (dppm) (dppm = Ph 2 PCH 2 PPh 2 ) ( 2 ) were prepared by reactions of ( μ -PDT)Fe 2 (CO) 6 ( A ) or [( μ -SCH 2 ) 2 NCH 2 CO 2 Me]Fe 2 (CO) 6 ( B ) with dppb or dppm in the presence of the decarbonylating agent Me 3 NO∙2H 2 O in MeCN at room temperature. Complex 1 was characterized by elemental analysis, IR, and 1 H ( 31 P, 13 C) NMR spectroscopic techniques. In addition, the molecular structures of 1 and 2 have been confirmed by single crystal X-ray diffraction analysis. In the crystal structure of 1 , two phosphorus atoms of dppb reside in a basal position of the square-pyramidal coordination sphere of the Fe2 and Fe3 atoms. However, in the crystal structure of 2 , P1 atom of dppm resides in an apical position of the square-pyramidal coordination sphere of the Fe2 atom.