Synthesis, characterization and some properties of mononuclear Ni and trinuclear NiFe2 complexes related to the active site of [NiFe]-hydrogenases.
The [N(2)S(2)]-type ligand 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) is prepared in 84% yield by a new method and its structure has been confirmed by X-ray crystallography. The new synthetic method involves sequential reaction of 1,2-phenylenedithiol with EtONa followed by treatment of the resulting disodium salt of 1,2-phenylenedithiol with in situ generated 2-(chloromethyl)pyridine from its HCl salt. Further treatment of ligand L with NiCl(2)·6H(2)O or NiI(2) affords the expected new mononuclear Ni complexes Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) and Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3) in 87-88% yields, whereas reaction of L with NiBr(2) under similar conditions results in formation of the expected new mononuclear complex Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) and one unexpected new mononuclear complex Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*) in 82% and 5% yields, respectively. More interestingly, the ligand L-containing novel trinuclear NiFe(2) complex Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) is found to be prepared by sequential reaction of (μ-S(2))Fe(2)(CO)(6) with Et(3)BHLi, followed by treatment of the resulting (μ-LiS)(2)Fe(2)(CO)(6) with mononuclear complex 1, 2, or 3 in 12-20% yields. The new complexes 1-4 and 2* are fully characterized by elemental analysis and various spectroscopies, and the crystal structures of 1, 2* and 3 as well as some electrochemical properties of 1-4 are also reported.
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China. lcsong@nankai.edu.cn
Li-Cheng
LC
Song
Xiao-Jing
XJ
Sun
Pei-Hua
PH
Zhao
Jia-Peng
JP
Li
Hai-Bin
HB
Song
D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D020134:Catalytic Domain; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007501:Iron / Q000737:chemistry*; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*
D056831:Coordination Complexes; D009532:Nickel; D007501:Iron; C043296:nickel-iron hydrogenase; D006864:Hydrogenase