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. 
                        more » 
                        « less   
                    This content will become publicly available on December 30, 2025
                            
                            Electronic Desymmetrization of Cu 3 (μ 3 -E) Clusters (E = S, Se) Induced by Edge-to-Face π-Stacking Interactions in the Second Coordination Sphere
                        
                    - Award ID(s):
- 1834750
- PAR ID:
- 10578060
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 63
- Issue:
- 52
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 24501 to 24505
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            MOF NU-1000 was employed to host Ni tripodal complexes prepared from new organometallic precursors [HNi(κ4(E,P,P,P)-E(o-C 6 H 4 CH 2 PPh 2 ) 3 ], E = Si (Ni-1), Ge (Ni-2). The new heterogenous catalytic materials, Ni-1@NU-1000 and Ni-2@NU-1000 show the advantages of both homogenous and heterogeneous catalysts. They catalyze the hydroboration of aldehydes and ketones more efficiently than the homogenous Ni-1 and Ni-2, under aerobic conditions, and allowing recyclability of the catalyst.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
