Abstract
A unique family of zwitterionic alkali-metal silanides of general formula [Si(SiMe2OR)3M] (M-3), where M = Li, Na, K and R = CH2CH3 (M-3b), CH(CH3)2 (M-3c), CH2CH(CH3)2 (M-3d), CH2CH2OSCH3 (M-3g), CH2CH2N(CH3)2 (M-3h), have been synthesized and their structures fully characterized. Compounds M-3 were prepared from reactions of the corresponding alkali-metal alkoxides, R′OM (R′ = But, Bui M = Li, Na, K) with the silanes Si(SiMe2OR)4 (2a-h), where R = CH2CH3 (b), CH(CH3)2 (c), CH2CH(CH3)2 (d), CH2CH2OSCH3 (g), CH2CH2N(CH3)2 (h), via selective Si-Si bond cleavage. Analysis of the X-ray data of Li-3a-e,g, Li-h, Li-4, Na-3a-c,e,f,h, and K-3b,d,e,g revealed two major structural motifs in the solid state: infinite chain type and monomeric zwitterions. The reaction of Si(SiMe2OCH2CH3)3Li (Li-3b) with BPh3 in THF gave the zwitterionic Lewis acid-base complex Ph3BSi(SiMe2OCH2CH3)3Li·THF (Li-5b). Reactions of W(CO)6 with Li-3b-d and Na-3b,c resulted in the formation of the zwitterionic silyl tungstenate complexes (CO)5WSi[SiMe2OCH2CH3]3Li (Li-6b), (CO)5WSi[SiMe2OCH(CH3)2]3Li (Li-6c), (CO)5WSi[SiMe2OCH2CH(CH3)2)]3Li (Li-6d), (CO)5WSi(SiMe2OCH2CH3)3Na (Na-6b), and (CO)5WSi[SiMe2OCH(CH3)2]3Na (Na-6c), respectively. The solid-state structures of Li-5b and Na-6b were determined by X-ray crystallography.
Original language | English |
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Pages (from-to) | 9869-9879 |
Number of pages | 11 |
Journal | Inorganic Chemistry |
Volume | 56 |
Issue number | 16 |
DOIs | |
Publication status | Published - 21 Aug 2017 |
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Zwitterionic Alkali-Metal Silanides of Tripodal Ligand Geometry: Synthesis, Structure, and Lewis Acid-Base Chemistry (crystallography dataset)
Thalangamaarachchige, V. D. (Creator), Li, H. (Creator), Cordes, D. B. (Creator), Unruh, D. K. (Creator) & Krempner, C. (Creator), Cambridge Crystallographic Data Centre, 1 May 2014
https://dx.doi.org/10.5517/ccdc.csd.cc12l381 and 11 more links, https://dx.doi.org/10.5517/ccdc.csd.cc12l392, https://dx.doi.org/10.5517/ccdc.csd.cc12l3b3, https://dx.doi.org/10.5517/ccdc.csd.cc12l3c4, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdg4, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdh5, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdj6, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdk7, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdl8, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdm9, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdnb, https://dx.doi.org/10.5517/ccdc.csd.cc1nmdpc (show fewer)
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