Further studies on reactions of organic halides with disilanes catalysed by transition metal complexes

Element−Element Addition to Alkynes Catalyzed by the Group 10 Metals

“…104 Eaborn found that the reaction of the bis(hydrosilane) 72 with Pt(H 2 CdCH 2 )(PPh 3 ) 2 gave complex 73 by oxidative addition (Scheme 100). 105 The same type of reaction led to the formation of the Pt complexes cis-Pt(SiMePh 2 ) 2 (PMe 2 Ph) 2 and cisPt(SiMe 2 Cl) 2 (PMe 2 Ph) 2 . The reaction of phenylacetylene with the former complex led to a complex containing phenylacetylene as a ligand.…”

Preparation of Methylphenyldichlorosilane through a Catalytic Cracking Reaction of 1,2-Dimethyl-1,1,2,2-Tetrachlorodisilane with Halobenzene

“…It was found that the reaction did not occur when Pd/C, PdCl 2 or RuCl 3 (entries 1-6) were used as catalysts, because they behaved as heterogeneous catalytic systems in this reaction. However, when Rh, Ru and Pd triphenylphosphine compounds (entries [8][9][10][11][12][13][14] were used, the catalysts dissolved in the reaction medium. The contact was expanded between catalyst and reactants, leading to the more complete reaction, so the conversion of Cl 2 MeSiSiMeCl 2 and selectivity to MePhSiCl 2 were higher than for heterogeneous catalysts under similar conditions.…”

“…7 1,2-dimethyl-1,1,2,2-tetrachlorodisilane (MeCl 2 SiSiCl 2 Me) is one of the methylchlorodisilanes (MCDS) which are by-products of high-boiling residues produced from the "direct process" 8 for the preparation of methylchlorosilanes. 9,10 The main methods of converting the MCDS into commercially valuable products reported in the literature are the catalytic cracking reactions of MCDS with RX (R is H, Me, Ph, PhCH 2 , etc., X is Cl, Br) [11][12][13][14][15][16][17][18] to form functional chlorosilicon monomers. Eaborn et al 11 reported that p-O 2 NC 6 H 4 CH 2 SiMe 3 or p-NCC 6 H 4 CH 2 SiMe 3 were prepared by Me 3 SiSiMe 3 reacting with benzyl halides catalysed by Pd(PAr 3 ) 4 (Ar=Ph, p-MeOC 6 H 4 and p-Me 3 SiCH 2 C 6 H 4 , etc.).…”

“…9,10 The main methods of converting the MCDS into commercially valuable products reported in the literature are the catalytic cracking reactions of MCDS with RX (R is H, Me, Ph, PhCH 2 , etc., X is Cl, Br) [11][12][13][14][15][16][17][18] to form functional chlorosilicon monomers. Eaborn et al 11 reported that p-O 2 NC 6 H 4 CH 2 SiMe 3 or p-NCC 6 H 4 CH 2 SiMe 3 were prepared by Me 3 SiSiMe 3 reacting with benzyl halides catalysed by Pd(PAr 3 ) 4 (Ar=Ph, p-MeOC 6 H 4 and p-Me 3 SiCH 2 C 6 H 4 , etc.). However, the benzyltrimethylsilanes were only formed in low yield in the process of silylanisation of benzyl halides, because a strong electron-withdrawing group could not be formed.…”

Stabile Stammlösungen von Silicium‐Grignard‐Reagenzien: Anwendung in eisen‐ und cobaltkatalysierten radikalischen C(sp3)‐Si‐Kreuzkupplungsreaktionen

“…[3, 4b,7c,d] Wirentschieden uns allerdings dafür, 6 in einer weniger etablierten Kohlenstoff-Silicium-Bindungsknüpfungsreaktion auszutesten, nämlich der übergangsmetallkatalysierten C(sp 3 )-Si-Kreuzkupplung zwischen nichtaktivierten Alkylelektrophilen und Siliciumnukleophilen. [10][11][12][13] Fu und Mitarbeiter [10] sowie wir selbst [11,12] hatten kürzlich Lçsungen fürd iese schwierige Umsetzung vorgestellt, die entweder R 3 SiZnCl 3 in einer nickelkatalysierten Kupplung von Alkylbromiden [10] oder R 3 SiBpin 5 in kupferkatalysierten Kupplungen von Alkyliodiden nutzen. [11,14] [10] und CuSCN [11] waren nicht oder deutlich weniger effektiv (Nr.…”