Abstract
DFT calculations within the two-component quasirelativistic approach and further analysis of 103Rh NMR shielding (including the natural bond orbitals method) in a series of flat-square complex anions cis-[X1X2Rh(CO)2]− (X1, X2 = Cl, Br, I) are used to determine the role of relativistic spin-orbit effects in 103Rh NMR shielding in these systems. Electron delocalization observed in these complexes provides the possibility of relativistic spin-orbit effects but complicates the interpretation of 103Rh NMR shielding in terms of chemically meaningful fragments of electronic system (lone pairs, chemical bonds).
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Acknowledgments
The authors express their sincere thanks to M. Ryzhikov for his technical support with the computer cluster used for our calculations and to A. Igoshkin for his criticism of aesthetic issues of the figures and the text of the article.
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Russian Text © The Author(s), 2019, published in Zhurnal Strukturnoi Khimii, 2019, Vol. 60, No. 11, pp. 1821–1828.
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Mirzaeva, I.V., Kozlova, S.G. The Nature of Halogen Dependence of 103Rh NMR Chemical Shift in Complex Anions cis-[X1X2Rh(CO)2]− (X1, X2 = Cl, Br, I). J Struct Chem 60, 1750–1756 (2019). https://doi.org/10.1134/S0022476619110076
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DOI: https://doi.org/10.1134/S0022476619110076