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Title: Structures and Energetics of E 2 H 3 + (E = As, Sb, and Bi) Cations
Award ID(s):
2153978
PAR ID:
10486152
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
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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  1. Abstract

    Coordination complexes of general formulatrans‐[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 ofDas 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 initioquantum 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.

     
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