Mononuclear, Dinuclear, and Trinuclear Iron Complexes
Featuring a New Monoanionic SNS Thiolate Ligand
Uttam
K. Das
Stephanie L. Daifuku
Serge I. Gorelsky
Ilia Korobkov
Michael L. Neidig
Jennifer J. Le
Roy
Muralee Murugesu
R. Tom Baker
10.1021/acs.inorgchem.5b02833.s003
https://acs.figshare.com/articles/dataset/Mononuclear_Dinuclear_and_Trinuclear_Iron_Complexes_Featuring_a_New_Monoanionic_SNS_Thiolate_Ligand/2086738
The
new tridentate ligand, S<sup><i>Me</i></sup>N<sup><i>H</i></sup>S = 2-(2-methylthiophenyl)benzothiazolidine,
prepared in a single step from commercial precursors in excellent
yield, undergoes ring-opening on treatment with Fe(OTf)<sub>2</sub> in the presence of base affording a trinuclear iron complex, [Fe<sub>3</sub>(μ<sub>2</sub>-S<sup><i>Me</i></sup>NS<sup>–</sup>)<sub>4</sub>](OTf)<sub>2</sub> (<b>1</b>) which is fully characterized by structural and spectroscopic methods.
X-ray structural data reveal that <b>1</b> contains four S<sup><i>Me</i></sup>NS<sup>–</sup> ligands meridionally
bound to two pseudooctahedral iron centers each bridged by two thiolates
to a distorted tetrahedral central iron. The combined spectroscopic
(UV–vis, Mössbauer, NMR), magnetic (solution and solid
state), and computational (DFT) studies indicate that <b>1</b> includes a central, high-spin Fe(II) (<i>S</i> = 2) with
two low-spin (<i>S</i> = 0) peripheral Fe(II) centers. Complex <b>1</b> reacts with excess PMePh<sub>2</sub>, CNxylyl (2,6-dimethylphenyl
isocyanide), and P(OMe)<sub>3</sub> in CH<sub>3</sub>CN to form diamagnetic,
thiolate-bridged, dinuclear Fe(II) complexes {[Fe(μ-S<sup><i>Me</i></sup>NS<sup>–</sup>)L<sub>2</sub>]<sub>2</sub>}(OTf)<sub>2</sub> (<b>2</b>–<b>4</b>).
These complexes are characterized by elemental analysis; <sup>1</sup>H NMR, IR, UV–vis, and Mössbauer spectroscopy; and
single crystal X-ray diffraction. Interestingly, addition of excess
P(OMe)<sub>3</sub> to complex <b>1</b> in CH<sub>2</sub>Cl<sub>2</sub> produces primarily the diamagnetic, mononuclear Fe(II) complex,
{Fe(S<sup><i>Me</i></sup>NS<sup>–</sup>)[P(OMe)<sub>3</sub>]<sub>3</sub>}(OTf) (<b>5</b>).
2016-01-19 00:00:00
Trinuclear Iron Complexes Featuring
New Monoanionic SNS Thiolate LigandThe
1 H NMR
IR
UV
Complex 1
CH 2Cl
DFT
spectroscopic methods
tridentate ligand
form diamagnetic
CH 3CN
trinuclear iron
pseudooctahedral iron centers