Journal
INORGANIC CHEMISTRY
Volume 48, Issue 17, Pages 8317-8324Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic900939c
Keywords
-
Categories
Funding
- NSF [CHE-0421116, CHE-0518508, CHE-0809603]
- Ursinus College
- [MCB-0424494]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0809603] Funding Source: National Science Foundation
Ask authors/readers for more resources
The synthesis and structure of the pseudotetrahedral, sulfur-rich, high-spin organoiron(II) [phenyltris((tert-butylthio)methyl)borate]Fe(Me), [PhTt(tBu)]Fe(Me), 1, are reported. Low-temperature Mossbauer spectroscopic studies reveal an isomer shift of delta = 0.60(3) mm/s and Delta E-Q = 0.00(1) mm/s and an S = 2 ground multiplet with a negative zero-field splitting, D = -33(3) cm(-1), E/D approximate to 0.01. The small separation of the ground doublet, Delta approximate to 0.01 cm(-1), allows for observation of X-band EPR signals at g(eff) approximate to 10 (g(z) = 2.6, g(x,y) = 2.00). The relatively large negative zero-field splitting and a highly anisotropic magnetic hyperfine tensor, containing a large orbital z component, {-10(4), -10(4), +33.8(2) MHz}, are concordant with the presence of unquenched orbital angular momentum. Density functional theory (DFT) calculations predict that the lowest-lying orbitals have predominantly d(xy)- and d(x2-y2)-like character, separated by an energy gap small enough to allow mixing through spin-orbit coupling, to generate a negative zero-field splitting, consistent with the experimental observations. The experimental and DFT-calculated isomer shifts are in good agreement (delta(calcd) = 0.5 mm/s). The unusual (for a high-spin ferrous site) null electric field gradients can be qualitatively explained in the frame of the spin-orbit coupling mixing. The very small Fermi contact component of the magnetic hyperfine tensor (A(FC)(exp) = -9 MHz) is not well described by the DFT approach (A(FC)(calcd) = +2 MHz). To our knowledge, this is the first study of a sulfur-coordinated high-spin organoiron(II) complex.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available