Electronic Structure of trans-[VIICl2(E(CH3)2CH2CH2E(CH3)2)2], E=N, P

Jafari MG, Zolnhofer E, Fehn D, Heinemann FW, Opalade AA, Carroll PJ, Meyer K, Krzystek J, Ozarowski A, Mindiola DJ, Jackson TA, Telser J (2024)

Publication Type: Journal article

Publication year: 2024

Journal

DOI: 10.1002/ejic.202400395

Abstract

Coordination complexes of general formula trans-[MX2(R2ECH2CH2ER2)2] (M^II=Ti, V, Cr, Mn; E=N or P; R=alkyl or aryl) are a cornerstone of coordination and organometallic chemistry. We investigate the electronic properties of two such complexes, trans-[VCl2(tmeda)2] and trans-[VCl2(dmpe)2], which thus represent trans-[MX2(R2ECH2CH2ER2)2] where M=V, X=Cl, R=Me and E=N (tmeda) and P (dmpe). These V^II complexes have S=3/2 ground states, as expected for octahedral d³. Their tetragonal distortion leads to zero-field splitting (zfs) that is modest in magnitude (D≈0.3 cm⁻¹) relative to analogous S=1 Ti^II and Cr^II complexes. This parameter was determined from conventional EPR spectroscopy, but more effectively from high-frequency and -field EPR (HFEPR) that determined the sign of D as negative for the diamine complex, but positive for the diphosphine, which information had not been known for any trans-[VX2(R2ECH2CH2ER2)2] systems. The ligand-field parameters of trans-[VCl2(tmeda)2] and trans-[VCl2(dmpe)2] are obtained using both classical theory and ab initio quantum chemical theory. The results shed light not only on the electronic structure of V^II in this environment, but also on differences between N and P donor ligands, a key comparison in coordination chemistry.

Authors with CRIS profile

Involved external institutions

Roosevelt University United States (USA) (US) University of Kansas (KU) United States (USA) (US) University of Pennsylvania United States (USA) (US) Florida State University (FSU) United States (USA) (US)

How to cite

APA:

Jafari, M.G., Zolnhofer, E., Fehn, D., Heinemann, F.W., Opalade, A.A., Carroll, P.J.,... Telser, J. (2024). Electronic Structure of trans-[VIICl2(E(CH3)2CH2CH2E(CH3)2)2], E=N, P. European Journal of Inorganic Chemistry. https://doi.org/10.1002/ejic.202400395

MLA:

Jafari, Mehrafshan G., et al. "Electronic Structure of trans-[VIICl2(E(CH3)2CH2CH2E(CH3)2)2], E=N, P." European Journal of Inorganic Chemistry (2024).

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