Multinuclear NMR study of the crystal field strength of the nitro ligand and the empirical estimation of the sup 59 Co NMR chemical shifts of cobalt-nitro complexes

Journal Article · Wed Oct 10 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00177a005· OSTI ID:6082059

Au-Yeung, S C.F.; Kwong, K W ^[1]; Buist, R J ^[2]

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1. Chinese Univ. of Hong Kong, Shatin (Hong Kong)
2. National Research Council, Ottawa, Ontario (Canada)

The variable ligand field strength of the nitro ligand has been reexamined on the basis of a steric model. An improved empirical method is proposed for the estimation of nitro ligand field strength in terms of a single correction parameter {Delta}{sub s} (1.824 {times} 10{sup {minus}6} ppm{sup {minus}1}) to the shift parameter S{sub NO{sub 2}} (3.075 {times} 10{sup {minus}5} ppm{sup {minus}1}) for the estimation of the {sup 59}Co NMR chemical shifts of cobalt-nitro complexes. The reversed chemical shift trend of geometrical isomers of cobalt-nitro complexes are attributed to variations in the 10Dq of the nitro ligands. The model is applied to the assignment of different isomers of cobalt-nitro compounds obtained from ligand exchange reactions of the cobaltinitrite anion with the N{sub 3}{sup {minus}} and SCN{sup {minus}} ions. In all the ligand exchange reactions studied, it was found that mixed nitro complexes formed in the reaction predominately adopted the trans configuration.

• OSTI ID: 6082059
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:21; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COBALT 59
COBALT COMPLEXES
COBALT ISOTOPES
COMPLEXES
CRYSTAL FIELD
DATA
EXPERIMENTAL DATA
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGANDS
MAGNETIC RESONANCE
NITRO COMPOUNDS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RESONANCE
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES