Metal-Ligand Cooperativity Promoting Sulfur Atom Transfer in Ferrous Complexes and Isolation of a Sulfurmethylenephosphorane Adduct
Sorsche D, Miehlich M, Zolnhofer E, Carroll PJ, Meyer K, Mindiola DJ (2018)
Publication Type: Journal article
Publication year: 2018
Journal
Book Volume: 57
Pages Range: 11552-11559
Journal Issue: 18
DOI: 10.1021/acs.inorgchem.8b01599
Abstract
The reaction of elemental sulfur with the cis-divacant octahedral complex [(pyrr2py)Fe(OEt2)] (1; pyrr2py2- = 3,5-tBu2-bis(pyrrolyl)pyridine) yields the iron dimer [(pyrr-1-S-pyrrpy)Fe]2 (2; pyrr-1-S-pyrrpy2- = 3,5-(tBu2-pyrrolyl)(1-S-3,5-tBu2-pyrrolyl)pyridine) resulting from a pyrr2py2- ligand based S-oxidation of one pyrrole arm. Addition of the phosphorus ylide H2CPPh3 to 1 forms the ylide adduct [(pyrr2py)Fe(CH2PPh3)] (3), which upon reaction with elemental sulfur produces a rare example of a sulfurmethylenephosphorane adduct, [(pyrr2py)Fe(SCH2PPh3)] (4). The sulfur-oxidized pyrrole group of the ligand pyrr-1-S-pyrrpy2- can be reversed, since complex 2 exhibits S atom transferability via the addition of 2 equiv of H2CPPh3 to yield a mixture of compounds 3 and 4. For all complexes reported, the ferrous ion remains S = 2. Complexes 2-4 were characterized by single-crystal X-ray diffraction as well as 1H NMR spectroscopy, solid and solution magnetic studies, and 57Fe Mössbauer spectroscopic measurements.
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APA:
Sorsche, D., Miehlich, M., Zolnhofer, E., Carroll, P.J., Meyer, K., & Mindiola, D.J. (2018). Metal-Ligand Cooperativity Promoting Sulfur Atom Transfer in Ferrous Complexes and Isolation of a Sulfurmethylenephosphorane Adduct. Inorganic Chemistry, 57(18), 11552-11559. https://doi.org/10.1021/acs.inorgchem.8b01599
MLA:
Sorsche, Dieter, et al. "Metal-Ligand Cooperativity Promoting Sulfur Atom Transfer in Ferrous Complexes and Isolation of a Sulfurmethylenephosphorane Adduct." Inorganic Chemistry 57.18 (2018): 11552-11559.
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