Coordination complexes of general formula
Structures and Energetics of E 2 H 3 + (E = As, Sb, and Bi) Cations
- Award ID(s):
- 2153978
- PAR ID:
- 10486152
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 128
- Issue:
- 3
- ISSN:
- 1089-5639
- Format(s):
- Medium: X Size: p. 563-571
- Size(s):
- p. 563-571
- Sponsoring Org:
- National Science Foundation
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Abstract trans ‐[MX2(R2ECH2CH2ER2)2] (MII=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] andtrans ‐[VCl2(dmpe)2], which thus representtrans ‐[MX2(R2ECH2CH2ER2)2] where M=V, X=Cl, R=Me and E=N (tmeda) and P (dmpe). These VIIcomplexes haveS =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 analogousS =1 TiIIand CrIIcomplexes. This parameter was determined from conventional EPR spectroscopy, but more effectively from high‐frequency and ‐field EPR (HFEPR) that determined the sign ofD as negative for the diamine complex, but positive for the diphosphine, which information had not been known for anytrans ‐[VX2(R2ECH2CH2ER2)2] systems. The ligand‐field parameters oftrans ‐[VCl2(tmeda)2] andtrans ‐[VCl2(dmpe)2] are obtained using both classical theory andab initio quantum chemical theory. The results shed light not only on the electronic structure of VIIin this environment, but also on differences between N and P donor ligands, a key comparison in coordination chemistry.