ISSN:
0749-1581
Keywords:
NMR
;
103Rh
;
31P
;
13C
;
rhodoximes
;
organobis(dimethylglyoximato) rhodium
;
complexes
;
trans influence
;
coupling constants
;
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The 103Rh NMR chemical shifts of rhodoximes [Rh(dmgH)2(PPh3)X] (1) and organorhodoximes [Rh(dmgH)2(L)R] (2, L = PPh3; 3, L = PMe3; 4, L = P(OPh)3; 5, L = SMe2; 6, L = py) were measured with a wide range of anionic ligands X, organo groups R and axial ligands L. The chemical shifts δ(103Rh) in the halide complexes 1 show the ‘normal halogen dependence’ (Cl 〉 Br 〉 I). δ(103Rh) in 2-6 depends on the axial base L in the order py 〉 SMe2 〉 PPh3 〉 P(OPh)3 ≍ PMe3 and in 2 on the organo group R in the order Et ≍ Me 〈 nPr 〈 CH2Ph ≍ CH2OMe 〈 CH2Br 〈 CH2Cl 〈 iPr 〈 Cy 〈 CH=CH2 〈 CH2SiMe3 〈 tBu 〈 cis-CH=CHPh ≍ cis-CH=CHPr 〈 Ph ≍ C≡CPh 〈 CPr=CH2. The coupling constants 1J(103Rh,31P) in 2 reflect the (NMR) trans influence of R. There is a strong correspondence between the NMR trans influence and the structural trans influence, as indicated by the bond lengths d(Rh - P).
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1260331209
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