Photoactivation of cobalt carbonyl catalysts: generation of reactive mononuclear fragments from dinuclear, metal-metal bonded complexes
Photoactivation of cobalt carbonyl catalysts: generation of reactive mononuclear fragments from dinuclear, metal-metal bonded complexes
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羰基钴催化剂的光活化：从双核金属-金属键配合物生成反应性单核片段
DOI：
10.1021/ja00516a058
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发表时间：
1979
影响因子：
15
通讯作者：
M. Wrighton
中科院分区：
文献类型：
--
作者：
Carol L. Reichel;M. Wrighton
摘要 : 金属-金属键配合物 (CO2(CO)6L2) (l = p(n-Bu)3, P(OPh)3) 和 Fe(n5-C5H5) (CO)2CO)(CO)3(P(OPh)3)) 均发生有效的（355 nm 处 θ 大于 0.1）光化学金属-金属键断裂，产生反应性 17 价电子 (CO(CO)3L)碎片。在 1-戊烯存在下，没有发现烯烃异构化，L = P(n-Bu)3； L = P(OPh)3 或当 P(n-Bu)3 配合物在 P(OMe)3 存在下受到辐射时，发现较低但显着的光催化活性。当在氢化物源 HSiEt3 存在下进行照射时，Co(CO)3L) 前体的活性显着提高。观察到烯烃异构化和正戊烷形成，以及少量含硅产物。独立于(Fe2(n的五次方-C5H5)(CO)2)光生自由基在迄今为止使用的任何条件下均不活跃。本申请中17价电子自由基的活性为Co(CO)3(P(OPh)3))Co(CO)3(P(n-Bu)3))Fe(n的五次方)功率-C5H5)(CO)2)。这些物质本身并不是有效的催化剂，但似乎确实与 HSiEt3 反应形成催化活性的单核 Co-氢化物络合物。 （作者）
Abstract : The metal-metal bonded complexes (CO2(CO)6L2) (l = p(n-Bu)3, P(OPh)3) and Fe(n5-C5H5) (CO)2CO)(CO)3(P(OPh)3)) all undergo efficient (theta greater than 0.1 at 355 nm) photochemical metal-metal bond cleavage to produce reactive 17-valence electron (CO(CO)3L) fragments. In the presence of 1-pentene no alkene isomerization is found for L = P(n-Bu)3; low, but significant, photocatalytic activity is found for L = P(OPh)3 or when the P(n-Bu)3 complex is irradiated in the presence of P(OMe)3. The Co(CO)3L) precursors are strikingly more active when irradiation is carried out in the presence of HSiEt3, a hydride source. Both alkene isomerization and n-pentane formation are observed, along with small quantities of Si-containing products. The Fe(n to the fifth power-C5H5)(CO)2) radical photogenerated independently from (Fe2(n to the fifth power-C5H5)2(CO)4 is not active under any conditons used thus far. The activity of 17-valence electron radicals in this application is Co(CO)3(P(OPh)3)) Co(CO)3(P(n-Bu)3)) Fe(n to the fifth power-C5H5)(CO)2). These species are not themselves effective catalysts but do seem to react with HSiEt3 to form catalytically active, mononuclear Co-hydride complexes. (Author)