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

Inorganic Chemistry American Chemical Society

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; pyrr2py^2- = 3,5-^tBu2-bis(pyrrolyl)pyridine) yields the iron dimer [(pyrr-1-S-pyrrpy)Fe]2 (2; pyrr-1-S-pyrrpy^2- = 3,5-(^tBu2-pyrrolyl)(1-S-3,5-^tBu2-pyrrolyl)pyridine) resulting from a pyrr2py^2- 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-pyrrpy^2- 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.

Authors with CRIS profile

Matthias Miehlich Lehrstuhl für Anorganische und Allgemeine Chemie Eva Zolnhofer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Pennsylvania

United States (USA) (US)

How to cite

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://dx.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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