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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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Substituent Effect on the Circularly Polarized Luminescence of C 1 ‐Symmetric Carbene‐Copper(I) Complexes
Abstract The substituent effect on the magnitude of the circularly polarized luminescence (CPL) ofMentCAAC‐Cu‐X (X=F, Cl, Br, I, BH4, B3H8; CAAC=cyclic (alkyl)(amino)carbenes) complexes is experimentally investigated. This study examines seven pairs of enantiomeric complexes with small anionic substituents (halides, borohydrides, hydride). The complexes are fully characterized, including single crystal X‐ray diffraction studies, and chiroptical measurements show that small covalent anions induce a larger CPL magnitude. These results demonstrate that the magnitude of the CPL can be manipulated without making any modifications to the chiral ligand.
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- Award ID(s):
- 2041084
- PAR ID:
- 10253965
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemPhotoChem
- Volume:
- 5
- Issue:
- 10
- ISSN:
- 2367-0932
- Format(s):
- Medium: X Size: p. 902-905
- Size(s):
- p. 902-905
- Sponsoring Org:
- National Science Foundation
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