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Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron–Sulfur Clusters – A New Class of Bioinspired Hydrogenase Models
Author(s) -
Kaiser Manuel,
Knör Günther
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500574
Subject(s) - chemistry , reactivity (psychology) , ferrocene , hydrogenase , sulfur , catalysis , derivative (finance) , polymer chemistry , organic chemistry , electrochemistry , medicine , alternative medicine , electrode , pathology , financial economics , economics
The air‐ and moisture‐stable iron–sulfur carbonyl clusters Fe 3 S 2 (CO) 7 (dppm) ( 1 ) and Fe 3 S 2 (CO) 7 (dppf) ( 2 ) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1′‐bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene‐bridged compound 1 and the ferrocene‐functionalized derivative 2 were determined by single‐crystal X‐ray diffraction. The catalytic reactivity of the trinuclear iron–sulfur cluster core for proton reduction in solution at low overpotential was demonstrated. These deeply colored bisphosphine‐bridged sulfur‐capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron‐based hydrogenases.