Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes
Cobalt(0) and Iron(0) Isocyanides as Catalysts for Alkene Hydrosilylation with Hydrosiloxanes
复制标题
钴(0)和铁(0)异氰化物作为氢硅氧烷与烯烃氢硅烷化反应的催化剂
DOI：
10.1021/acs.organomet.8b00389
复制
发表时间：
2018
期刊：
影响因子：
2.8
通讯作者：
H. Ngaashima
中科院分区：
文献类型：
--
作者：
A. Sanagawa;H. Ngaashima
铁和钴的异氰化物 Fe(CNR)5(1) 和 Co2(CNR)8(2)，其中 R = 叔丁基 (tBu)、金刚烷基 (Ad) 和异氰基丙酮 (Mes)，是通过 C8K 或二氧化硅-Na 在 CNR 存在下还原 FeBr2 或 CoI2 来制备的。这些配合物对烯烃与氢硅氧烷进行催化氢化硅烷化，并将结果与之前报道的 Fe(OPiv)2/CNAd 或 Co(OPiv)2/CNAd 催化剂体系获得的结果进行比较。 1 催化的烯丙醚与 1,1,1,3,3-五甲基二硅氧烷 (PMDS) 的氢化硅烷化以及 2 催化的几种烯烃与 PMDS 或 1,1,1,3,5,5,5-七甲基三硅氧烷 (MD'M) 的反应表现出比 Fe(OPiv)2 或 Co(OPiv)2/CNR 催化剂更高的催化活性系统。配合物 1 和 2 对于含 Si-H 基团的硅油的催化化学改性和双组分硅酮固化是有效的。在所有情况下，在金属异氰化物配合物和相应的M(OPiv) 2 /CNR催化剂体系之间，就通过氢化硅烷化形成所需产物和由于脱氢硅烷化形成副产物而言，反应的选择性没有差异。还研究了 1,2 和 M(OPiv)2/CNR 催化剂体系产生的催化活性物质。
Iron and cobalt isocyanides, Fe(CNR)5(1) and Co2(CNR)8(2), where R =t-butyl (tBu), adamantyl (Ad), and mesityl (Mes), were prepared by reduction of FeBr2or CoI2in the presence of CNR by C8K or silica-Na. These complexes were subjected to catalytic hydrosilylation of alkenes with hydrosiloxanes, and the results are compared with those obtained by previously reported Fe(OPiv)2/CNAd or Co(OPiv)2/CNAd catalyst systems. Hydrosilylation of allylic ethers with 1,1,1,3,3-pentamethyldisiloxane (PMDS) catalyzed by1and the reaction of several alkenes with PMDS or 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD′M) catalyzed by2exhibited greater catalytic activity than that observed for the Fe(OPiv)2or Co(OPiv)2/CNR catalyst system. Complexes1and2were effective for catalytic chemical modification of silicone fluids containing Si–H groups and for two-component silicone curing. In all cases, selectivity of the reaction in terms of formation of the desired product by hydrosilylation and of byproducts due to dehydrogenative silylation did not differ between the metal isocyanide complexes and the corresponding M(OPiv)2/CNR catalyst system. Catalytically active species generated from1,2, and the M(OPiv)2/CNR catalyst system were also investigated.