Monovalent iron in a sulfur-rich environment.
A series of low-coordinate, paramagnetic iron complexes in a tris(thioether) ligand environment have been prepared. Reduction of ferrous {[PhTt(tBu)]FeCl}2 [1; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate] with KC8 in the presence of PR3(R = Me or Et) yields the high-spin, monovalent iron phosphine complexes [PhTt(tBu)]Fe(PR3) (2). These complexes provide entry into other low-valent derivatives via ligand substitution. Carbonylation led to smooth formation of the low-spin dicarbonyl [PhTt(tBu)]Fe(CO)2 (3). Alternatively, replacement of PR 3 with diphenylacetylene produced the high-spin alkyne complex [PhTt(tBu)]Fe(PhCCPh) (4). Lastly, 2 equiv of adamantyl azide undergoes a 3 + 2 cycloaddition at 2, yielding high-spin dialkyltetraazadiene complex 5.
Mock
Michael T
MT
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Popescu
Codrina V
CV
Yap
Glenn P A
GP
Dougherty
William G
WG
Riordan
Charles G
CG
D000114:Acetylene / Q000737:chemistry; D002414:Cations, Monovalent; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D013455:Sulfur / Q000737:chemistry*; D014961:X-Ray Diffraction
D002414:Cations, Monovalent; D013455:Sulfur; D007501:Iron; D000114:Acetylene