18165-85-0Relevant articles and documents
Trinuclear μ3-Silyl Complexes of Ruthenium and Group 9 Metals Having 3c-2e Interactions and Transformation of a μ3-Silyl Complex of Ru2Ir into μ-Silyl and μ3-Silylene Complexes
Nagaoka, Masahiro,Shima, Takanori,Takao, Toshiro,Suzuki, Hiroharu
, p. 7232 - 7240 (2014)
μ3-Silyl complexes (CpRu)2(CpM)( μ3-H2SiR)( μ-H)3 (4, M = Co; 5, M = Rh; 6, M = Ir) were synthesized by the reaction of trinuclear heterometallic clusters of Ru and group 9 metals, (CpRu)2(
Photoreactions of silyliron(II) complexes Cp*Fe(CO)2SiMe3 (Cp* = η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes
Kawano, Yasuro,Tobita, Hiromi,Ogino, Hiroshi
, p. 125 - 143 (2007/10/02)
The photochemistry of silyliron(II) complexes Cp*Fe(CO)2SiMe3 (Cp* = η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes is described.Three types of products were observed, depending on the bulkiness of the Cp* ligands and the substituents on the trihydrosilanes: (η5-C5H5)Fe(CO)2SiMe3 reacts with tert-alkylsilanes RSiH3 (R = tBu, C(Me2)2H) upon irradiation to give silylene-bridged diiron complexes (η5-C5H5)2Fe2(CO)3(μ-SiHR) in good yields.In contrast, (η5-C5Me5)Fe(CO)2SiMe3 reacts with the tert-alkylsilanes photochemically to give silyl monoiron complexes (η5-C5Me5)Fe(CO)2SiH2R exclusively.Using p-TolSiH3 instead of tert-alkylsilane, the main photolysis product was the hydridobis(silyl)iron complex Cp*Fe(CO)SiMe3(H)SiH2-p-Tol.The X-ray crystal structure analysis of (η5-C5H5)2Fe2(CO)3(μ-SiHtBu) revealed that this complex adopts a geometry in which the two Cp rings and a Si-H bond are located on the same side with respect to the SiFe2C four-membered ring 29Si NMR spectra of the silylene-bridged diiron complexes showed signals at remarkably low field (δ 235.5-289.1 ppm).A mechanism for the formation of these silylene-bridged diiron complexes is proposed.
SILACYCLOHEXADIENYLANIONEN BIS- UND TRIS-(TRIMETHYLSILYL)-SILACYCLOHEXADIENE
Maerkl, G.,Hoellriegl, H.,Schlosser, W.
, p. 129 - 170 (2007/10/02)
1,1-Dialkyl(1,1-diaryl)-4-R-1-silacyclohexadienyl anions (1) are available by ether cleavage of the corresponding 1,1-dialkyl(1,1-diaryl)-4-methoxy-4-R-1-silacyclohexa-2,5-dienes (4), or by deprotonation of the 1,1-dialkyl(1,1-diaryl)-4-R-1-silacyclohexa-2,4-dienes (3) - which are available from 4 - with n-BuLi or LDA resp.The anions 1 are regioselectively silylated by trimethylchlorosilane to give the 6-trimethylsilyl-1-silacyclohexa-2,4-dienes (7,8), their alkylation or acylation occurs exclusively in 4-position to 16 or 17 resp.Deprotonation of 7, 8 with n-BuLi gives the 2-trimethylsilyl-1-silacyclohexadienyl anions (9), with trimethylchlorosilane they react regioselectively to give the 2,6-bis(trimethylsilyl)-1-silacyclohexa-2,4-dienes (10, 11), with alkyl halides and ketones the anion 9 reacts only in the 4-position.The 1-silacyclohexa-2,5-dienes 22, 25, 28 substituted at the silicon atom by functional groups (O-i-Prop) or by hydrogen can be transformed into 2,6-bis(trimethylsilyl)-1-silacyclohexa-2,4-dienes 24, 27, 33 resp., if LDA is used as base.The easily formed 4-R-2,6-bis(trimethylsilyl)-1-silacyclohexa-2,4-dienyl anions (by deprotonation of 10, 11, 24, 27, 33 with LDA) react with trimethylchlorosilane regioselectively to give 4-R-2,4,6-tris(trimethylsilyl)-1-silacyclohexa-2,5-dienes 37.Accessing 37 succeeds very simply by manifold-silylation of the 1-sila-2,4-cyclohexadienes 38 with excess trimethylchlorosilane in the presence of 3 mol LDA.Owing to trimethylsilyl substitution in the 2,6-position of the 1-silacyclohexa-2,4-dienes, the ring-silicon atom is strongly sterically shielded, therefore reactions of functional groups at the silicon atom are restricted.
