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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Bicyclic phosphines as ligands for cobalt catalysed hydroformylation. Crystal structures of [Co(phoban[3.3.1]-Q)(CO)(3)](2) (Q = C2H5, C5H11, C3H6NMe2, C6H11)
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Bicyclic phosphines as ligands for cobalt catalysed hydroformylation. Crystal structures of [Co(phoban[3.3.1]-Q)(CO)(3)](2) (Q = C2H5, C5H11, C3H6NMe2, C6H11)

机译：双环膦作为钴催化加氢甲酰化的配体。 [Co（phoban [3.3.1] -Q）（CO）（3）]（2）的晶体结构（Q = C2H5，C5H11，C3H6NMe2，C6H11）

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摘要

A range of tertiary bicyclic phosphine ligands derived from cis, cis-1,5-cyclooctadiene (Phoban family) was studied by batch autoclave reactions during the hydroformylation of a mixture of linear internal decenes using a cobalt catalyst system. Comparative runs were performed with PBu3 as representative of standard trialkyl phosphine behaviour. The Phoban ligands comprise of a cyclooctyl bicycle with a mixture of the [3.3.1] and [4.2.1] isomers where the third substituent was systematically varied, Phoban-Q (Q = CH2CH3, (CH2)(4)CH3, (CH2)(9)CH3, (CH2)(19)CH3, (CH2)(3)N(CH3)(2), C6H11 and C6H5). An increase in ligand concentration resulted in a decrease in the reaction rate while the selectivity towards the n-alcohol product increased in accordance with a move from more unmodified catalysis to more modified catalysis. Alcohol yields of 77-85% were obtained at rates of 1.8-2.4 h(-1) for highly modified catalysis. Under highly modified conditions the linearity of the alcohol ranges in a narrow band from similar to 85-90% from Phoban-Ph to Phoban-Cy respectively. Hydrogenation of the alkene substrate varied from similar to 9-15% for Phoban-Ph and Phoban-Cy respectively the least and most electron donating derivatives. The two phosphine isomers were separated for Phoban-C-2 and the hydroformylation activity were re-evaluated for each isomer. The less electron donating [4.2.1] isomer required slightly higher ligand concentrations to achieve fully modified catalysis and gave rates and linearities comparable to the [3.3.1] isomer but giving slightly higher yields due to less hydrogenation of the olefin. In comparison, at fully modified conditions, PBu3 gave a rate of 0.6 h(-1), alcohol yield of 77%, linearity of 81% and 17% hydrogenation. The crystal structures of the cobalt dimers [Co(CO)(3)(Phoban[3.3.1]-C-2)](2), [Co(CO)(3)(Phoban[3.3.1]-C-5)](2), [Co(CO)(3)(Phoban[3.3.1]-C3NMe2)](2), and [Co(CO)(3)(Phoban[3.3.1]-Cy)](2) have been determined and indicated very similar geometries with Co-Co and Co-P bond distances ranging from 2.6526(10)-2.707(3) and 2.1963(8)-2.2074(9) angstrom respectively. The cone angles of the Phoban ligands were calculated from the crystallographic data, according to the Tolman model, and ranges from 159-165 degrees.
机译：在使用钴催化剂体系对线性内部混合物的加氢甲酰化过程中，通过间歇高压釜反应研究了一系列源自顺式，顺式-1,5-环辛二烯的叔双环膦配体（Phoban家族）。用PBu3作为标准三烷基膦行为的代表进行比较试验。 Phoban配体由环辛基自行车和[3.3.1]和[4.2.1]异构体的混合物组成，其中第三个取代基有系统地变化，Phoban-Q（Q = CH2CH3，（CH2）（4）CH3，（ CH2）（9）CH3，（CH2）（19）CH3，（CH2）（3）N（CH3）（2），C6H11和C6H5）。配体浓度的增加导致反应速率降低，而对正醇产物的选择性根据从更未改性的催化向更改性的催化的转变而增加。对于高度修饰的催化，以1.8-2.4 h（-1）的速率可获得77-85％的酒精产量。在高度修饰的条件下，从Phoban-Ph到Phoban-Cy，醇的线性均在一个窄带内，分别约为85-90％。烯烃底物的氢化程度从Phoban-Ph和Phoban-Cy最小和最大的供电子衍生物分别约为9-15％。分离了两个膦异构体的Phoban-C-2，并对每种异构体的羰基化活性进行了重新评估。供电子量较少的[4.2.1]异构体需要略高的配体浓度才能实现完全改性的催化作用，并具有与[3.3.1]异构体相当的速率和线性，但由于烯烃的氢化反应较少，因此产率较高。相比之下，在完全改性的条件下，PBu3的合成速率为0.6 h（-1），醇产率为77％，线性度为81％，氢化率为17％。钴二聚体[Co（CO）（3）（Phoban [3.3.1] -C-2）]（2），[Co（CO）（3）（Phoban [3.3.1] -C- 5）]（2），[Co（CO）（3）（Phoban [3.3.1] -C3NMe2）]（2）和[Co（CO）（3）（Phoban [3.3.1] -Cy）] （2）已确定并表明非常相似的几何形状，Co-Co和Co-P键距分别为2.6526（10）-2.707（3）和2.1963（8）-2.2074（9）埃。根据托尔曼模型，根据晶体学数据计算出Phoban配体的锥角，范围为159-165度。

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