期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2008
卷号：105
期号：22
页码：7652-7657
DOI：10.1073/pnas.0800538105
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：The reaction of NiBr2(EtOH)4 with a 1:2-3 mixture of FeBr2(CO)4 and Na(SPh) generated a linear trinuclear Fe-Ni-Fe cluster (CO)3Fe({micro}-SPh)3Ni({micro}-SPh)3Fe(CO)3, 1, whereas the analogous reaction system FeBr2(CO)4/Na(StBu)/NiBr2(EtOH)4 (1:2-3:1) gave rise to a linear tetranuclear Fe-Ni-Ni-Fe cluster [(CO)3Fe({micro}-StBu)3Ni({micro}-Br)]2, 2. By using this tetranuclear cluster 2 as the precursor, we have developed a new synthetic route to a series of thiolate-bridged dinuclear Fe(CO)3-Ni complexes, the structures of which mimic [NiFe] hydrogenase active sites. The reactions of 2 with SC(NMe2)2 (tmtu), Na{S(CH2)2SMe} and ortho-NaS(C6H4)SR (R = Me, tBu) led to isolation of (CO)3Fe({micro}-StBu)3NiBr(tmtu), 3, (CO)3Fe(StBu)({micro}-StBu)2Ni{S(CH2)2SMe
