TY - JOUR
T1 - Synthesis and structure of a tungsten dichlorosilyl dihydride complex
AU - Sakaba, Hiroyuki
AU - Hirata, Takeshi
AU - Kabuto, Chizuko
AU - Kabuto, Kuninobu
N1 - Funding Information:
This work was supported by Grant-in-Aid for Scientific Research from the Minister of Education, Culture, Sports, Science and Technology.
PY - 2007/1/1
Y1 - 2007/1/1
N2 - The reaction of the donor-stabilized silylene complex cis-Cp*(CO)2(H)W{double bond, long}SiHPh · THF (3, Cp* = η5-C5Me5) with LiAlH4 followed by the protonation of the resulting Li[Cp*(CO)2W(H)(SiH2Ph)] (4) with excess CF3COOH afforded the trihydride complex Cp*(CO)2WH3 (6). The structure of 6 was characterized using variable-temperature NMR studies and X-ray crystal analysis. Deprotonation of 6 with KH gave the anionic dihydride complex K[Cp*(CO)2WH2] (7), which was converted into the dichlorosilyl dihydride complex Cp*(CO)2W(H)2(SiHCl2) (8) on treatment with trichlorosilane. The X-ray crystal analysis of 8 revealed that it adopts a distorted pseudo-octahedral structure with a short W-Si bond, long Si-Cl bonds, and short contacts between the hydrides and silicon atom. Along with these structural features, the conformation of the silyl ligand around the W-Si bond may suggest the presence of a double interligand hypervalent interaction between the dichlorosilyl and hydrides ligands.
AB - The reaction of the donor-stabilized silylene complex cis-Cp*(CO)2(H)W{double bond, long}SiHPh · THF (3, Cp* = η5-C5Me5) with LiAlH4 followed by the protonation of the resulting Li[Cp*(CO)2W(H)(SiH2Ph)] (4) with excess CF3COOH afforded the trihydride complex Cp*(CO)2WH3 (6). The structure of 6 was characterized using variable-temperature NMR studies and X-ray crystal analysis. Deprotonation of 6 with KH gave the anionic dihydride complex K[Cp*(CO)2WH2] (7), which was converted into the dichlorosilyl dihydride complex Cp*(CO)2W(H)2(SiHCl2) (8) on treatment with trichlorosilane. The X-ray crystal analysis of 8 revealed that it adopts a distorted pseudo-octahedral structure with a short W-Si bond, long Si-Cl bonds, and short contacts between the hydrides and silicon atom. Along with these structural features, the conformation of the silyl ligand around the W-Si bond may suggest the presence of a double interligand hypervalent interaction between the dichlorosilyl and hydrides ligands.
KW - Hydrides
KW - Interligand hypervalent interaction
KW - Silicon
KW - Tungsten
KW - X-ray crystallography
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U2 - 10.1016/j.jorganchem.2006.08.065
DO - 10.1016/j.jorganchem.2006.08.065
M3 - Article
AN - SCOPUS:33845673779
VL - 692
SP - 402
EP - 407
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-3
ER -