Investigation of phosphine donor properties to vanadium(V) nitrides

Results in Chemistry

Aaron L. Odom¹  Linqing Mo²  Hannah I. Barr² 

[1] Corresponding author at: Michigan State University, Department of Chemistry, 478 S. Shaw Ln, East Lansing, MI 48824, USA.;Department of Chemistry, Michigan State University, 578 S. Shaw Lane, East Lansing, MI 48824, USA;

关键词: Catalysis;    Modelling;    Ligand donor parameter;    Phosphines;    Vanadium;   

DOI  :  

来源: DOAJ

【 摘 要 】

Catalyst optimization has been greatly aided over the years by methods of characterizing donor and steric properties of ligands. Here, we investigated a vanadium model system, NV(NH2)2L, to determine if the enthalpic barriers associated with amide rotation are in a range that would make this a synthetic target for determining the donor ability of L experimentally, e.g., by spin saturation transfer of the amide protons in the 1H NMR. In addition to determining that the barriers to rotation should be amenable to this method, we investigated how various phosphine donor properties affected amide rotation for the d0 metal and contrasted this with a late transition metal system. The calculations suggest that some PX3 ligand features, such as lone pairs on the X substituent, may lead to increases in the high oxidation state system where they are electron withdrawing in the low oxidation state systems. The cause of this electronic difference was investigated using Natural Resonance Theory.

【 授权许可】

Unknown