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Diiron dithiolate complexes have received special attention because of their structural similarity to the active site of [FeFe]-hydrogenases, which are the most efficient and fastest catalysts for the generation of dihydrogen in nature. Recently, we established a novel and efficient way to prepare phosphinesubstituted diiron aza-and oxadithiolate complexes. Reaction of Fe 2 (μ-SCH 2 OH) 2 (CO) 6 and several phosphine ligands L (L = PPh 3 , PPh 2 (2-C 5 H 4 N), P(C 6 H 4 -4-CH 3 ) 3 ) affords the intermediate Fe 2 (μ-SCH 2 OH) 2 (CO) 5 L, while the intermediate in situ reacts with primary amines RNH 25 [PPh 2 (2-C 5 H 4 N)] (5), Fe 2 [(μ-SCH 2 ) 2 NCH 2 CH 2 CH 2 SCH 3 ](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (6), Fe 2 [(μ-SCH 2 ) 2 N C 6 H 4 -4-CH 3 ](CO) 5 [PPh 2 (2-C 5 H 4 N)] (7), and Fe 2 [(μ-SCH 2 ) 2 N C 6 H 4 -4-CH 3 ](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (8) in moderate yields. A novel complex Fe 2 [(μ-SCH 2 ) 2 NCH 2 CH 2 PPh 2 ](CO) 5 (9) can be obtained by reaction of Fe 2 (μ-SCH 2 OH) 2 (CO) 6 and Ph 2 PCH 2 CH 2 NH 2 . In addition, according to the same strategy, phosphine-substituted diiron oxadithiolate complexes Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 [P(C 6 H 4 -4-F) 3 ] (10), Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (11), and Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 (Ph 2 PCH 2 CH 3 ) ( 12) have been successfully synthesized. All of the new complexes 1−12 were fully characterized by elemental analysis, IR, and NMR spectroscopy, and particularly for 1−4, 6, 7, and 9−11 by X-ray single diffraction analysis. Moreover, complexes 1 and 10 were found to be catalysts for H 2 production under electrochemical conditions.

Eight new O-alkyldithiophosphato nickel complexes 1-8 with chelating aminodiphosphine ligands have been successfully synthesized in moderate yields by the treatment of O,O′-alkydithiophosphoric acid salts (R 1

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