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See Supporting Information.
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13844303302
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See Experimental Section for details.
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2 solution, no spin-spin couplings to the fluorine atoms were observed, suggesting fast intermolecular fluorine exchange for these cases also; see: Marat, R. K.; Janzen, A. F. Can. J. Chem. 1977, 55, 3845.
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19F NMR spectrum is consistent with a trigonal bipyramidal geometry about the silicon atom, having an intramolecular Si·N interaction; see: Breliere, C.; Carre, F.; Corriu, R. J. P.; De Saxce, A.; Poirier, M.; Royo, G. J. Organomet. Chem. 1981, 205, C1.
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(b) Other analogous examples for anionic hexacoordinate fluorosilicates are also known; see: Breliere, C.; Carre, F.; Corriu, R. J. P.; Douglas, W. E.; Poirier, M.; Royo, G.; Wong Chi Man, M. Organometallics 1992, 11, 1586 and references therein.
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13844277825
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15N two-bond spin-spin coupling was observed for the 1·2py complex in which the two py ligands are in trans position with respect to each other.3
-
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-
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24
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0000560483
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(b) The only other reported coupling across the Si·N coordinative bond is related to hexacoordinate silicon compounds having intramolecular Si·N bonds; see: Kalikhman, I.; Krivonos, S.; Stalke, D.; Kottke, T.; Kost, D. Organometallics 1997, 16, 3255.
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Unfortunately, many attempts to obtain crystals suitable for X-ray crystallography for the various complexes studied here from different solvent combinations and temperatures were unsuccessful. For the case of the larger bipy and phen ligands, forming the 1·bipy and 1·phen complexes, X-ray structures were previously reported.4 Other examples for X-ray structures of neutral compounds having intramolecular Si·N interaction are known.5 For examples, see: (a) Timosheva, N. V.; Chandrasekaran, A.; Day, R. O.; Holmes, R. R. Organometallics 2001, 20, 2331.
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