Syntheses of highly unsaturated isocyanides via organometallic pathways.
Syntheses of highly unsaturated isocyanides via organometallic pathways.
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通过有机金属途径合成高度不饱和异氰化物。
DOI：
10.1039/c1dt11382h
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发表时间：
2012
影响因子：
4
通讯作者：
D. Lentz
中科院分区：
文献类型：
--
作者：
Monika Mujkic;D. Lentz
锂或格氏化合物 2a-i 对 (CO)(5)Cr(CN-CF=CF(2)) 1 进行亲核攻击发生碳碳偶联反应，生成异氰化物配合物 (CO)(5)Cr(CN-CF=CF-R) 3a-i (a R = CH=CH(2), b R = CH=CF(2), c R = CeqCH, d R = CeqC-SiMe(3), e R = C=C-Ph、f R = C=C-C(6)F(4)OMe、g R = C=C-C(6)H(3)(CF(3))(2)、h R = C(6)F(5)、i R = C(6)H(3)(CF(3))(2)) 作为 E 和 Z 异构体的混合物。双核配合物5a-c由1与分别作为Z,Z-、E,Z-和E,E-异构体的二锂或二镁化合物4a-c反应获得。 (CO)(5)Cr(CN-CF=CF-C=C-C=C-CF=CF-NC)Cr(CO)(5)7 由 (CO)(5)Cr(CN-CF=CF-C=C-H 3d 通过 Eglington-Glaser 偶联得到 Z,Z-、Z,E- 和 E,E-异构体的混合物。 (CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)6 和 (CO)(5)Cr(CN-CF=CF-C=C-C≡C-CF=CF-NC)Cr(CO)(5)7 与八羰基二钴反应形成簇化合物Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] Z,Z-8, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,Z-8 和E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,E-8 和Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C−C−C−C−CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] E,Z-9 和E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C−C−C−CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9 分别通过以下公式阐明了 E-3d、Z-3h、Z,Z-8、E,Z-8 和 Z,Z-9 的晶体和分子结构。单晶X射线晶体学。
The carbon carbon coupling reaction by nucleophilic attack of (CO)(5)Cr(CN-CF=CF(2)) 1 by lithium or Grignard compounds 2a-i yields the isocyanide complexes (CO)(5)Cr(CN-CF=CF-R) 3a-i (a R = CH=CH(2), b R = CH=CF(2), c R = C≡CH, d R = C≡C-SiMe(3), e R = C≡C-Ph, f R = C≡C-C(6)F(4)OMe, g R = C≡C-C(6)H(3)(CF(3))(2), h R = C(6)F(5), i R = C(6)H(3)(CF(3))(2)) as mixtures of E and Z isomers. The dinuclear complexes 5a-c are obtained from the reaction of 1 with the dilithio or dimagnesium compound 4a-c as the Z,Z-, E,Z- and E,E-isomers, respectively. (CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)7 is obtained as a mixture of Z,Z-, Z,E- and E,E-isomers from (CO)(5)Cr(CN-CF=CF-C≡C-H 3d by Eglington-Glaser coupling. (CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)6 and (CO)(5)Cr(CN-CF=CF-C=C-C≡C-CF=CF-NC)Cr(CO)(5)7 react with octacarbonyldicobalt forming the cluster compounds Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] Z,Z-8, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,Z-8 and E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,E-8 and Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] E,Z-9 and E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9, respectively. The crystal and molecular structures of E-3d, Z-3h, Z,Z-8, E,Z-8 and Z,Z-9 were elucidated by single-crystal X-ray crystallography.