Preparation, characterization, electrochemical properties and single-crystal structural analysis of [Tc(SCP)2(DMPE)2](PF6)3, where scp is the Zwitter-ionic ligand −SCH2P+(CH3)2(CH2)2P(S)(CH3)2 and DMPE is 1,2-bis(dimethylphosphino)ethane

Okamoto, Ken‐ichi; Kirchhoff, Jon R.; Heineman, William R.; Deutsch, Edward; Heeg, Mary Jane

doi:10.1016/s0277-5387(00)81755-6

Cited by 10 publications

(1 citation statement)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Complex 4 represents a rare example of a sulfurmethylenephosphorane ligand bound to iron through the sulfur atom. 31,32 In this case, sulfur oxidation of the methylene carbon of the ylide atom occurred rather than oxidation of the iron center. At this point, however, we cannot refute the possibility of a species such as an Fe(IV) sulfido species, [(pyrr 2 py)Fe(S)(CH 2 PPh 3 )], undergoing reductive coupling of the sulfide and ylide to form the sulfurmethylenephosphorane ligand in 4.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

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

et al. 2018

View full text Add to dashboard Cite

The reaction of elemental sulfur with the cis-divacant octahedral complex [(pyrrpy)Fe(OEt)] (1; pyrrpy = 3,5-Bu-bis(pyrrolyl)pyridine) yields the iron dimer [(pyrr-1-S-pyrrpy)Fe] (2; pyrr-1-S-pyrrpy = 3,5-(Bu-pyrrolyl)(1-S-3,5-Bu-pyrrolyl)pyridine) resulting from a pyrrpy ligand based S-oxidation of one pyrrole arm. Addition of the phosphorus ylide HCPPh to 1 forms the ylide adduct [(pyrrpy)Fe(CHPPh)] (3), which upon reaction with elemental sulfur produces a rare example of a sulfurmethylenephosphorane adduct, [(pyrrpy)Fe(SCHPPh)] (4). The sulfur-oxidized pyrrole group of the ligand pyrr-1-S-pyrrpy can be reversed, since complex 2 exhibits S atom transferability via the addition of 2 equiv of HCPPh 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 H NMR spectroscopy, solid and solution magnetic studies, andFe Mössbauer spectroscopic measurements.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 97%