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In nonpolar or weakly polar aprotic solvents, such as hydrocarbons and ethers, which are suitable solvents for alkali metal silanides, the coinage metal halides are almost insoluble. Under such heterogenous conditions (and in the absence of phosphanes), we typically observed the formation of dark slurries that mainly contained metal powder and metal-free silanes rather than the formation of well-defined silyl complexes. Similar observations have also been made by others; see, for example: A. H. Cowley, T. M. Elkins, R. A. Jones, C. M. Nunn, Angew. Chem. 1988, 100, 1396;
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77951520986
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3, solution under ambient conditions; it crystallizes from this solution as a bright yellow crystalline material. The structure derived from a single crystal could be confirmed with previously obtained powder diffraction data. Further details of the crystal structure determination are given with the Supporting Information
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3, solution under ambient conditions; it crystallizes from this solution as a bright yellow crystalline material. The structure derived from a single crystal could be confirmed with previously obtained powder diffraction data. Further details of the crystal structure determination are given with the Supporting Information.
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13
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77951598654
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CCDC 751847-751854 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
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CCDC 751847-751854 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cit
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77951589275
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The mild oxidating agent pyridine-N-oxide undergoes no redox reaction when heated for 24 h with aurate 2 in boiling toluene (111°C). Instead, a crystalline pyridine-N-oxide solvate of 2 is obtained from this experiment in high yields
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The mild oxidating agent pyridine-N-oxide undergoes no redox reaction when heated for 24 h with aurate 2 in boiling toluene (111°C). Instead, a crystalline pyridine-N-oxide solvate of 2 is obtained from this experiment in high yields.
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77951563920
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Overviews on structures and bonding in ligand-stabilized gold clusters: a) P. J. Jones, Gold Bull. 1983, 16, 115;
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Jones, P.J.1
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77951546556
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Bond indices were calculated on experimental structures using the NBO 3.0 module implemented in Gaussian03 Revision D.01, M. J. Frisch, et al. Complete citations can be found in the Supporting Information
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Bond indices were calculated on experimental structures using the NBO 3.0 module implemented in Gaussian03 Revision D.01, M. J. Frisch, et al. Complete citations can be found in the Supporting Information.
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29
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77951575133
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The tetraaurate 6 had also been obtained as diethyl ether and toluene solvates; the potassium cations are coordinated by a solvent molecule, thus preventing further agostic interactions. Details are given in the Supporting Information
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The tetraaurate 6 had also been obtained as diethyl ether and toluene solvates; the potassium cations are coordinated by a solvent molecule, thus preventing further agostic interactions. Details are given in the Supporting Information.
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30
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33746304398
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For silylene anion radicals, see: a) D. Bravo-Zhivotovskii. I. Ruderfer, S. Melamed, M. Botoshansky, B. Tumanskii, Y. Apeloig, Angew. Chem. 2005, 117, 749;
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Bravo-Zhivotovskii, D.1
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b) S. Inoue, M. Ichinohe, A. Sekiguchi, J. Am. Chem. Soc. 2007, 129, 6096.
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Inoue, S.1
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35
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77951547591
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A closer inspection of the hypersurface revealed a further very shallow minimum in between mini and min2 that corresponds to loosely bonded van der Waals complexes of the starting compounds. Further details are given in the Supporting Information
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A closer inspection of the hypersurface revealed a further very shallow minimum in between mini and min2 that corresponds to loosely bonded van der Waals complexes of the starting compounds. Further details are given in the Supporting Information.
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37
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77951551182
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Augmenting the basis sets of silicon and gold with diffuse and polarization functions leads to even smaller barriers for the metathesis. For R = R′ = R″ = Me, the formation of the adduct min2 is then calculated to be even slightly exergonic. Detailed information is given in the Supporting Information
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Augmenting the basis sets of silicon and gold with diffuse and polarization functions leads to even smaller barriers for the metathesis. For R = R′ = R″ = Me, the formation of the adduct min2 is then calculated to be even slightly exergonic. Detailed information is given in the Supporting Information.
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