192822-77-8Relevant academic research and scientific papers
Sodium diarylbismuthide as a reagent for the bismuthanation of reactive arenes. Application to the synthesis of mixed triarylbismuthanes bearing a substituent group incompatible with Grignard and organolithium reagents
Rahman, Mizanur,Matano, Yoshihiro,Suzuki, Hitomi
, p. 3565 - 3568 (2008/10/08)
Several mixed triarylbismuthanes bearing an electron-withdrawing functionality, such as the nitro, carbonyl, or ester group, which are inaccessible by the conventional methods based on organometallic reagents such as Grignard and organolithium compounds, are synthesized in low to acceptable yields by the reaction of in situ generated sodium diarylbismuthide with iodoarenes or arenediazonium tetrafluoroborates.
Linear trimeric, dimeric, and monomeric titanium(III) aryloxides
Minhas, Ravinder,Duchateau, Robbert,Gambarotta, Sandro,Bensimon, Corinne
, p. 4933 - 4938 (2008/10/08)
Reactions of trans-Ti(TMEDA)2Cl2 (TMEDA = N,N,N′,N′-tetramethylethylenediamine) with 2 equiv of RONa [R = Ph, 3,5-(t-Bu)2C6H3] formed the paramagnetic light-green linear trimeric Ti(III) derivative Ti3(PhO)9-(TMEDA)2 (1) and the pink dimeric complex [Ti(RO)Cl(TMEDA)]2(μ-OR)2 [R = 3,5-(t-Bu)2C6H3] (2), respectively. Complex 1 could also be conveniently synthesized from TiCl3(THF)3 and PhONa in the presence of TMEDA. Conversely, complex 2 could be obtained from TiCl3(THF)3 only when the reaction was carried out in toluene, since bright-yellow crystals of the mononuclear anionic complexes [Ti(RO)2(TMEDA)Cl2][M′] [M′ = Na(TMEDA)2+ (3a), 1/2(TMEDA)H+ (3b)] were isolated when the reaction was performed in THF. Reaction of Ti[N(SiMe3)2]3 with 3 equiv of 2,6-Me2C6H3OH in toluene led to the formation of the first dinuclear homoleptic complex [Ti(RO)3]2 [R = 2,6-Me2C6H3 (4)], which was isolated as green-blue crystals. A similar reaction with the more bulky 2,6-(i-Pr)2C6H3OH led to the formation of the neutral homoleptic Ti(IV) species Ti[OC6H3-2,6-(i-Pr)2]4 (6). Conversely, the anionic homoleptic complex {Ti[OC6H3-2,6-(i-Pr)2] 4}{Li(TMEDA)2}·toluene (7) was obtained by reacting the corresponding lithium phenoxide with TiCl3(THF)3. The structures of 1, 3b, and 4 were determined by X-ray analysis. Crystal data are as follows. 1: monoclinic, C2/c, a = 14.758 (5) A?, b = 21.920 (2) A?, c = 11.855 (1) A, β = 102.339 (4)°, V = 6274 (7) A?3, Z = 4, R = 0.058 Rw = 0.024) for 417 parameters and 2425 significant reflections out of 4648. 3b: triclinic, P1, a = 12.877 (2) A?, b = 16.850 (3) A?, c = 12.605 (2) A?, α = 106.65 (1)°, β = 100.65 (1)°, γ = 68.63 (1)°, V = 2430.4 (7) A?3, Z = 2, R = 0.080 (Rw, = 0.081) for 435 parameters and 4685 significant reflections out of 7234. 4: triclinic, P1, a = 11.372 (3) A?, b = 11.458 (3) A?, c = 10.859 (4) A?, α = 117.04 (2)°, β = 115.29 (3)°, γ = 93.56 (4)°, V = 1080.1 (9) A?3, Z = 2, R = 0.036 (Rw = 0.051) for 362 parameters and 3297 significant reflections out of 4020.
