A New Pyridine-substituted Azadithiolate 2Fe2S Complex Related to the Active Site of [FeFe]-hydrogenase

A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H+）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H+ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.