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Metal–Ligand Cooperativity Promoting Sulfur Atom Transfer in Ferrous Complexes and Isolation of a Sulfurmethylenephosphorane Adduct

Journal Article · · Inorganic Chemistry
 [1];  [2];  [2];  [3];  [2];  [3]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States); Program Manager, Catalysis Science Office of Basic Energy Sciences U.S. Department of Energy
  2. Freidrich Alexander Univ. Erlangen-Nürnberg (FAU), Erlangen (Germany)
  3. Univ. of Pennsylvania, Philadelphia, PA (United States)
+ Show Author Affiliations
Here, 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.
Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
DOE Contract Number:
SC0012486; FG02-07ER15893
OSTI ID:
1843656
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 18 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ligands
Mathematical methods
Oligomers
Pyrroles
Sulfur