Synthesis and characterization of diiron dithiolate complexes containing a quinoxaline bridge

Fenfen Xu, Shaowu Du, Yuping Liu, Jacqueline Hassan, Jie Zhang, Alan Bond

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12 Citations (Scopus)

Abstract

A potential model complex for the hydrogenase active site, [Fe(2) (mu-CH(2)S)(2)R (CO)(6)] (1) (R = quinoxaline), was synthesized by condensation of [(mu-LiS)(2)Fe(2)(CO)(6)] with 2,3-bis(bromomethyl)-quinoxaline. Reactions of 1 with bis(diphenylphosphino)methane (dppm) under a range of conditions yielded substituted complexes [Fe(2) (mu-CH(2)S)(2)R (CO)(5)(dppm)] (2), [Fe(2) (mu-CH(2)S)(2)R (CO)(4)(k(2)-dppm)] (3) and [Fe(2) (mu-CH(2)S)(2)R (CO)(4)(mu-dppm)] (4). X-ray crystallography confirms that in 2, the dppm is terminally bonded to an iron atom via one phosphorus atom, whereas in 3, it acts as a chelating ligand to coordinate to an iron center in a dibasal-substituted manner. In 4, the dppm bridges the two iron atoms in a cis basal/basal fashion with one phosphorus bonded to each iron atom. Treatment of 1 with various tertiary phosphines at room temperature in acetonitrile (MeCN) generates a range of mono-substituted products [Fe(2) (mu-CH(2)S)(2)R (CO)(5)L] (5, L = PEt(3); 6, PMe(3); 7, PPh(3); 8, Me(2)PPh). With Bu NC, mono- and di-substituted [Fe(2) (mu-CH(2)S)(2)R (CO)(5)(Bu NC)] (9) and [Fe(2) (mu-CH(2)S)(2)R (CO)(4)(-) (Bu NC)(2)] (10) complexes are generated. All the complexes were characterized by elemental analysis, IR, MS and NMR spectroscopy. IR and NMR spectroscopic studies suggest that addition of excess HBF(4)center dot OEt(2) acid to 1-4 led to the protonation of quinoxaline nitrogen atoms. In contrast, 5-10 were not stable in acidic media. Electrochemistry of 1-4 was investigated in the acetonitrile medium (0.1 M Bu(4)NPF(6)). The electrochemical instability of the reduced ligand, quinoxaline, and the reduced forms of these complexes revealed from the electrochemical studies suggests that they do not provide ideal models of the hydrogenase active site.
Original languageEnglish
Pages (from-to)10907 - 10917
Number of pages11
JournalDalton Transactions
Volume40
Issue number41
DOIs
Publication statusPublished - 2011

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