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Title: As-P vs. P-P Insertion in AsP 3 : Kinetic Control of the Formation of [AsP 3 NO] +: As-P vs. P-P Insertion in AsP 3 : Kinetic Control of the Formation of [AsP 3 NO] +
NSF-PAR ID:
10103097
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
European Journal of Inorganic Chemistry
Volume:
2019
Issue:
21
ISSN:
1434-1948
Page Range / eLocation ID:
p. 2607-2612
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. High-resolution X-ray diffraction experiments, theoretical calculations and atom-specific X-ray absorption experiments were used to investigate two nickel complexes, (MePh 3 P) 2 [Ni II (bdtCl 2 ) 2 ]·2(CH 3 ) 2 SO [complex (1)] and (MePh 3 P)[Ni III (bdtCl 2 ) 2 ] [complex (2)]. Combining the techniques of nickel K - and sulfur K -edge X-ray absorption spectroscopy with high-resolution X-ray charge density modeling, together with theoretical calculations, the actual oxidation states of the central Ni atoms in these two complexes are investigated. Ni ions in two complexes are clearly in different oxidation states: the Ni ion of complex (1) is formally Ni II ; that of complex (2) should be formally Ni III , yet it is best described as a combination of Ni 2+ and Ni 3+ , due to the involvement of the non-innocent ligand in the Ni— L bond. A detailed description of Ni—S bond character (σ,π) is presented. 
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