A study of ortho- and para-siloxyanilines for the synthesis of mono-, bi-, and tetra-nuclear early transition metal–imido complexes
摘要:
The siloxyanilines o-Me(3)SiOC(6)H(4)NH(2) (1) and p-RMe(2)SiOC(6)H(4)NH(2) (R = H (2); R = Me (3)), and their N-silylated derivatives p-Me(3)SiOC(6)H(4)NHSiMe(3) (4) and p-Me(3)SiOC(6)H(4)N(SiMe(3))(2) (5) have been prepared from ortho- or para-aminophenol and used in the synthesis of imido complexes. Thus, binuclear [{Ti(eta (5)-C(5)H(5))Cl} {mu -NC(6)H(4)(p-OSiMe(3))}](2) (6) and mononuclear [TiCl(2){NC(6)H(4)(p-OSiMe(3))}(py)(3)] (7) imido complexes have been obtained from the reaction of 3 and [Ti(eta (5)-C(5)H(5))Cl(3)] or [TiCl(2)(N'Bu)(py)(3)], respectively. In contrast, the reaction of 1 with TiCl(4) and 'Bupy affords the titanocycle [TiCl(2){OC(6)H(4)(o-NH)-N,O}('Bupy)(2)] (8). Compound 5 has also been used to prepare the niobium imide complex [NbCl(3){NC(6)H(4)(p-OSiMe(3))}(MeCN)(2)] (9), by its reaction with NbCl(5) in CH(3)CN. These findings have been applied to the synthesis of polynuclear systems. Thus, chlorocarbosilane Si[CH(2)CH(2)CH(2)Si(Me)(2)Cl], (CS-Cl) has been functionalized with the ortho- and para-aminophenoxy groups to give 10 and 11, respectively. The use of 11 has allowed the formation of the tetranuclear compound 12. Attempts to synthesize terminal imido titanium complexes from 10 and TiCl(4) in the presence of 'Bupy and Et(3)N, give complex 8 and carbosilane CS-Cl. (C) 2000 Elsevier Science S.A. All rights reserved.
A study of ortho- and para-siloxyanilines for the synthesis of mono-, bi-, and tetra-nuclear early transition metal–imido complexes
摘要:
The siloxyanilines o-Me(3)SiOC(6)H(4)NH(2) (1) and p-RMe(2)SiOC(6)H(4)NH(2) (R = H (2); R = Me (3)), and their N-silylated derivatives p-Me(3)SiOC(6)H(4)NHSiMe(3) (4) and p-Me(3)SiOC(6)H(4)N(SiMe(3))(2) (5) have been prepared from ortho- or para-aminophenol and used in the synthesis of imido complexes. Thus, binuclear [{Ti(eta (5)-C(5)H(5))Cl} {mu -NC(6)H(4)(p-OSiMe(3))}](2) (6) and mononuclear [TiCl(2){NC(6)H(4)(p-OSiMe(3))}(py)(3)] (7) imido complexes have been obtained from the reaction of 3 and [Ti(eta (5)-C(5)H(5))Cl(3)] or [TiCl(2)(N'Bu)(py)(3)], respectively. In contrast, the reaction of 1 with TiCl(4) and 'Bupy affords the titanocycle [TiCl(2){OC(6)H(4)(o-NH)-N,O}('Bupy)(2)] (8). Compound 5 has also been used to prepare the niobium imide complex [NbCl(3){NC(6)H(4)(p-OSiMe(3))}(MeCN)(2)] (9), by its reaction with NbCl(5) in CH(3)CN. These findings have been applied to the synthesis of polynuclear systems. Thus, chlorocarbosilane Si[CH(2)CH(2)CH(2)Si(Me)(2)Cl], (CS-Cl) has been functionalized with the ortho- and para-aminophenoxy groups to give 10 and 11, respectively. The use of 11 has allowed the formation of the tetranuclear compound 12. Attempts to synthesize terminal imido titanium complexes from 10 and TiCl(4) in the presence of 'Bupy and Et(3)N, give complex 8 and carbosilane CS-Cl. (C) 2000 Elsevier Science S.A. All rights reserved.
Synthesis of (η6-arene)(η5-cyclopentadienyl) iron (II) complexes with heteroatom and carbonyl substituents. Part I: Oxygen and carbonyl substituents
作者:R.M.G. Roberts
DOI:10.1016/j.jorganchem.2005.12.070
日期:2006.6
used to introduce oxygen substituents into (η-arene)(η-cyclopentadienyl) iron (II) complexes. Photochemical ligand exchange led to the formation of the first recorded trioxygenated complex as well as mono- and di-oxygenated species. Using microwave techniques, reaction times for SNAr displacement reactions of halobenzene complexes by phenols were reduced from several hours to a few minutes. Phenols protected
已使用一系列反应将氧取代基引入(η-芳烃)(η-环戊二烯基)铁(II)络合物中。光化学配体交换导致形成第一个记录的三加氧配合物以及单加氧和双加氧物质。使用微波技术,通过苯酚进行卤代苯配合物的S N Ar置换反应的反应时间从数小时减少至数分钟。苯酚受任一t保护使用常规的热配体交换反应,发现-丁基化或三甲基甲硅烷基化产生适量的相应酚配合物。没有这种保护,收率极低。上述方法导致二羟基苯配合物的第一实例的合成。还报告了一些其他合成方法。
HAPKOH A. L.; BAXMUTOV V. I.; KARAPETYAN SH. A.; KALACHEV A. I.; VALETSKI+, IZV. AN CCCP. CEP. XIM., 1979, HO 5, 1090-1093
作者:HAPKOH A. L.、 BAXMUTOV V. I.、 KARAPETYAN SH. A.、 KALACHEV A. I.、 VALETSKI+
DOI:——
日期:——
A study of ortho- and para-siloxyanilines for the synthesis of mono-, bi-, and tetra-nuclear early transition metal–imido complexes
作者:J.M Benito、Silvia Arévalo、E de Jesús*、F.J de la Mata、J.C Flores*、R Gómez
DOI:10.1016/s0022-328x(00)00391-0
日期:2000.9
The siloxyanilines o-Me(3)SiOC(6)H(4)NH(2) (1) and p-RMe(2)SiOC(6)H(4)NH(2) (R = H (2); R = Me (3)), and their N-silylated derivatives p-Me(3)SiOC(6)H(4)NHSiMe(3) (4) and p-Me(3)SiOC(6)H(4)N(SiMe(3))(2) (5) have been prepared from ortho- or para-aminophenol and used in the synthesis of imido complexes. Thus, binuclear [Ti(eta (5)-C(5)H(5))Cl} mu -NC(6)H(4)(p-OSiMe(3))}](2) (6) and mononuclear [TiCl(2)NC(6)H(4)(p-OSiMe(3))}(py)(3)] (7) imido complexes have been obtained from the reaction of 3 and [Ti(eta (5)-C(5)H(5))Cl(3)] or [TiCl(2)(N'Bu)(py)(3)], respectively. In contrast, the reaction of 1 with TiCl(4) and 'Bupy affords the titanocycle [TiCl(2)OC(6)H(4)(o-NH)-N,O}('Bupy)(2)] (8). Compound 5 has also been used to prepare the niobium imide complex [NbCl(3)NC(6)H(4)(p-OSiMe(3))}(MeCN)(2)] (9), by its reaction with NbCl(5) in CH(3)CN. These findings have been applied to the synthesis of polynuclear systems. Thus, chlorocarbosilane Si[CH(2)CH(2)CH(2)Si(Me)(2)Cl], (CS-Cl) has been functionalized with the ortho- and para-aminophenoxy groups to give 10 and 11, respectively. The use of 11 has allowed the formation of the tetranuclear compound 12. Attempts to synthesize terminal imido titanium complexes from 10 and TiCl(4) in the presence of 'Bupy and Et(3)N, give complex 8 and carbosilane CS-Cl. (C) 2000 Elsevier Science S.A. All rights reserved.