Reactions of co-ordinated ligands. Part 54. Synthesis of (1,2,3-η)-trans-butadienyl complexes by deprotonation or desilylation of cationic molybdenum 1,3-diene complexes; formation of η<sup>4</sup>-vinylketene complexes and crystal structures of [Mo{(1,2,3-η)-trans-CH<sub>2</sub>CHCCH<sub>2</sub>}(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)], [Mo{η<sup>3</sup>-CH<sub>2</sub>CC(Me)CH<sub>2</sub>CO}(CO)<sub>2</sub>(η-C<sub>5</sub>Me<sub>5</sub>)] and [Mol{η<sup>4</sup>-CH<sub>2</sub>CHC(Me)CO}(CO)(η-C<sub>5</sub>Me<sub>5</sub>)]
作者:Stephen A. Benyunes、Robert J. Deeth、Arno Fries、Michael Green、Mary McPartlin、Caroline B. M. Nation
DOI:10.1039/dt9920003453
日期:——
[NBun4]F with the cation [Moη4-CH2CHC(SiEt3)CH2}(CO)2(η-C5Me5)][BF4]. The desilylation reaction has also been used to transform [Moη4-syn-CH(Ph)CHC(SiMe3)CH2}(CO)2(η-C5Me5)][BF4] into a mixture of exo- and endo-[Mo(1,2,3-η)-trans-syn-CH(Ph)CHCCH2}(CO)2(η-C5Me5)]. An alternative synthetic route to (1,2,3-η)-trans-butadienyl complexes was explored involving reaction of Li[Mo(CO)3(η-C5Me5)] with CH2CC(Me)CH2Cl
一个基座的Li [N(森的反应的产物的3)2 ]与[沫(η 4 -C 4 H ^ 6)(CO)2(η-C 5我5)] [BF 4 ]是外-orientated(1,2,3-η) -反式-butadienyl络合物[沫(1,2,3-η) -反式-CH 2 CHC CH 2 }(CO)2(η-C 5我5) ]。后者的单晶X射线衍射研究表明,两个相邻的π系统,烯丙基和C CH 2丁二烯片段中的α彼此正交。该复合物可以通过下述物质反应[NBU选择性和高收率形成Ñ 4 f让阳离子[沫η] 4 -CH 2 CHC(SIET 3)CH 2 }(CO)2(η-C 5我5) ] [BF 4 ]。的脱甲硅烷基反应也被用于转化[沫η 4 -顺式-CH(PH)CHC(森达3)CH 2 }(CO)2(η-C 5我5)] [BF 4 ]成的混合物exo-和内- [钼(1,2,3-η) -反式-顺式-CH(PH)CHC