Thalangamaarachchige Vidura D, Li Hui, Cordes David B, Unruh Daniel K, Krempner Clemens
Department of Chemistry & Biochemistry, Texas Tech University , Box 1061, Lubbock, Texas 79409-1061, United States.
Inorg Chem. 2017 Aug 21;56(16):9869-9879. doi: 10.1021/acs.inorgchem.7b01227. Epub 2017 Jul 31.
A unique family of zwitterionic alkali-metal silanides of general formula [Si(SiMeOR)M] (M-3), where M = Li, Na, K and R = CHCH (M-3b), CH(CH) (M-3c), CHCH(CH) (M-3d), CHCHOSCH (M-3g), CHCHN(CH) (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' = Bu, Bu; M = Li, Na, K) with the silanes Si(SiMeOR) (2a-h), where R = CHCH (b), CH(CH) (c), CHCH(CH) (d), CHCHOSCH (g), CHCHN(CH) (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(SiMeOCHCH)Li (Li-3b) with BPh in THF gave the zwitterionic Lewis acid-base complex PhBSi(SiMeOCHCH)Li·THF (Li-5b). Reactions of W(CO) with Li-3b-d and Na-3b,c resulted in the formation of the zwitterionic silyl tungstenate complexes (CO)WSi[SiMeOCHCH]Li (Li-6b), (CO)WSi[SiMeOCH(CH)]Li (Li-6c), (CO)WSi[SiMeOCHCH(CH))]Li (Li-6d), (CO)WSi(SiMeOCHCH)Na (Na-6b), and (CO)WSi[SiMeOCH(CH)]Na (Na-6c), respectively. The solid-state structures of Li-5b and Na-6b were determined by X-ray crystallography.
合成了通式为[Si(SiMeOR)M] (M - 3)的一类独特的两性离子碱金属硅化物，其中M = Li、Na、K，R = CHCH (M - 3b)、CH(CH) (M - 3c)、CHCH(CH) (M - 3d)、CHCHOSCH (M - 3g)、CHCHN(CH) (M - 3h)，并对其结构进行了全面表征。化合物M - 3由相应的碱金属醇盐R'OM (R' = Bu、Bu；M = Li、Na、K)与硅烷Si(SiMeOR) (2a - h)反应制备，其中R = CHCH (b)、CH(CH) (c)、CHCH(CH) (d)、CHCHOSCH (g)、CHCHN(CH) (h)，通过选择性的Si - Si键断裂反应得到。对Li - 3a - e,g、Li - h、Li - 4、Na - 3a - c,e,f,h和K - 3b,d,e,g的X射线数据分析揭示了固态中的两种主要结构模式：无限链型和单体两性离子。Si(SiMeOCHCH)Li (Li - 3b)与BPh在THF中反应生成两性离子路易斯酸碱络合物PhBSi(SiMeOCHCH)Li·THF (Li - 5b)。W(CO)与Li - 3b - d和Na - 3b,c反应分别生成两性离子硅钨酸盐络合物(CO)WSi[SiMeOCHCH]Li (Li - 6b)、(CO)WSi[SiMeOCH(CH)]Li (Li - 6c)、(CO)WSi[SiMeOCHCH(CH))]Li (Li - 6d)、(CO)WSi(SiMeOCHCH)Na (Na - 6b)和(CO)WSi[SiMeOCH(CH)]Na (Na - 6c)。通过X射线晶体学确定了Li - 5b和Na - 6b的固态结构。
