TY - JOUR
T1 - Zwitterionic Alkali-Metal Silanides of Tripodal Ligand Geometry
T2 - Synthesis, Structure, and Lewis Acid-Base Chemistry
AU - Thalangamaarachchige, Vidura D.
AU - Li, Hui
AU - Cordes, David B.
AU - Unruh, Daniel K.
AU - Krempner, Clemens
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/8/21
Y1 - 2017/8/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85027709389&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.7b01227
DO - 10.1021/acs.inorgchem.7b01227
M3 - Article
C2 - 28758741
AN - SCOPUS:85027709389
SN - 0020-1669
VL - 56
SP - 9869
EP - 9879
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -