Modelling nucleophilic substitution at silicon using solution 19F NMR chemical shift, 1JSi‑F and 2JC‑F coupling constant data of pentacoordinate silicon compounds. Correlation with other magnetic nuclei and X-ray structures,

Bassindale, Alan R.; Baukov, Yuri I.; Borbaruah, Moheswar; Glynn, Simon J; Negrebetsky, Vadim V.; Parker, David J.; Taylor, Peter G. and Turtle, Robert (2003). Modelling nucleophilic substitution at silicon using solution 19F NMR chemical shift, 1JSi‑F and 2JC‑F coupling constant data of pentacoordinate silicon compounds. Correlation with other magnetic nuclei and X-ray structures,. Journal of Organometallic Chemistry, 669(1-2) pp. 154–163.

DOI: https://doi.org/10.1016/S0022-328X(03)00009-3

Abstract

Solution 1JSi---F and 2JC---F NMR coupling constant and 19F-NMR chemical shift data have been analysed in a series of pentacoordinate silyl monofluoride complexes used to model nucleophilic substitution at silicon. Patterns in the data reveal strong correlations between both coupling constants and 19F-NMR chemical shifts and the degree of substitution displayed by each. Excellent correlation is obtained between the new data and our previous 13C- and 29Si-NMR studies to further confirm the validity of the NMR technique for structural correlation in solution. By pooling the X-ray crystal structures of a large number of compounds of this class from both our own results and the literature we are able to provide a possible explanation for some of the trends in the NMR data we observe in solution.

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