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The six\u2010membered FeSCECS rings in these complexes (E=Ge or Sn) adopt an unusual conformation with nearly co\u2010planar SCECS atoms perpendicular to the Fe\u2010Fe core. Computational modelling traces this result to the steric interaction of the Me groups with the axial carbonyls of the Fe<jats:sub>2<\/jats:sub>(CO)<jats:sub>6<\/jats:sub> cluster and low torsional strain for GeMe<jats:sub>2<\/jats:sub> and SnMe<jats:sub>2<\/jats:sub> moieties owing to the long C\u2212Ge and C\u2212Sn bonds. Gas\u2010phase photoelectron spectroscopy of these complexes shows a shift of ionization potentials to lower energies with substantial sulfur orbital character and, as supported by the computations, an increase in sulfur character in the predominantly metal\u2013metal bonding HOMO. Cyclic voltammetry reveals that the complexes follow an ECE\u2010type reduction mechanism (E=electron transfer and C=chemical process) in the absence of acid and catalysis of proton reduction in the presence of acid. Two cyclic tetranuclear complexes featuring the sulfur atoms of two Fe<jats:sub>2<\/jats:sub>S<jats:sub>2<\/jats:sub>(CO)<jats:sub>6<\/jats:sub> cores bridged by CH<jats:sub>2<\/jats:sub>SnR<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>, R=Me, Ph, linkers were also obtained and characterized.<\/jats:p>","DOI":"10.1002\/chem.201603843","type":"journal-article","created":{"date-parts":[[2016,10,13]],"date-time":"2016-10-13T03:40:32Z","timestamp":1476330032000},"page":"346-359","source":"Crossref","is-referenced-by-count":47,"title":["[FeFe]\u2010Hydrogenase H\u2010Cluster Mimics with Unique Planar \u03bc\u2010(SCH<sub>2<\/sub>)<sub>2<\/sub>ER<sub>2<\/sub> Linkers (E=Ge and Sn)"],"prefix":"10.1002","volume":"23","author":[{"given":"Hassan","family":"Abul\u2010Futouh","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie Friedrich-Schiller-Universit\u00e4t Jena  Humboldt Str. 8 07743 Jena Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Laith R.","family":"Almazahreh","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie Friedrich-Schiller-Universit\u00e4t Jena  Humboldt Str. 8 07743 Jena Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takahiro","family":"Sakamoto","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry The University of Arizona  Tucson AZ 85721 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nhu Y. 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