Synthetic and structural study on some new porphyrin or metalloporphyrin macrocycle-containing model complexes for the active site of [FeFe]-hydrogenases

To mimick the natural enzymes [FeFe]-hydrogenases, some new porphyrin and metalloporphyrin moiety-containing model complexes, namely 5-[p-Fe-2(CO)(6)(mu-SCH2)(2)CHO2CC6H4],10,15,20-triphenylporphyrin (2), 5-[p-Fe-2(CO)(6)(mu-SCH2)(2)CHO2CC6H4],10,15,20-triphenylporphyrinozinc (3), 5-[p-Fe-2(CO)(6)(mu-SCH2)(2)NC2H4SC6H4], 10,15,20-triphenylporphyrin (7), and 5-[p-Fe-2(CO)(5)(mu-SCH2)(2)NC2H4SC6H], 10,15,20-triphenylpor phyrin (8), have been successfully prepared by our designed synthetic routes involving the corresponding precursor compounds [(m-SCH2)(2)CHO2CC6H4CHO-p]Fe-2(CO)(6) (1), p-Boc-NHC2H4SC6H4CHO (4), 5-(p-Boc-NHC2H4SC6H4), 10,15,20-triphenylporphyrin (5), and 5-(p-NH2C2H4SC6H4), 10,15,20-triphenylpor phyrin (6). All these new compounds 1-8 have been characterized by elemental analysis and various spectroscopic methods, and particularly for 1-3 and 7 by X-ray crystallography. In addition, the density functional theory computations on 8 were performed to assist its structural characterization. (C) 2013 Elsevier B. V. All rights reserved.