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Synthesis of Base-Stabilized Hydrido(hydroborylene)tungsten Complexes and Their Reactions with Terminal Alkynes To Give η3-Boraallyl Complexes
Organometallics ( IF 2.5 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/acs.organomet.7b00723 Zeping Hui 1 , Takahito Watanabe 1 , Hiromi Tobita 1
Organometallics ( IF 2.5 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/acs.organomet.7b00723 Zeping Hui 1 , Takahito Watanabe 1 , Hiromi Tobita 1
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Reaction of the methyl(pyridine)tungsten complex Cp*(CO)2W(py)Me with borane–NHC (NHC = N-heterocyclic carbene; MeIMe, MeIiPr) (MeIMe = 1,3,4,5-tetramethylimidazol-2-ylidene, MeIiPr = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) adducts gave the NHC-stabilized hydrido(hydroborylene)tungsten complexes Cp*(CO)2W(H)(BH·NHC) (1a: NHC = MeIMe, 1b: NHC = MeIiPr) as dark brown crystals in high yields accompanied by liberation of pyridine and methane. X-ray crystal structure analysis revealed that the W–B bond of 1b is bridged by a hydrido ligand. Reactions of 1a,b with phenylacetylene at room temperature afforded NHC-stabilized η3-boraallyl complexes 2a,b, respectively, through a new type of hydroboration of the alkyne triple bond: i.e., addition of a hydrogen and a borylene. Reaction of 1a with 3-butyn-2-one also led to hydroboration of the triple bond, not the C═O double bond, to give η3-boraallyl complex 3. In the reaction of 1a with (trimethylsilyl)acetylene, 1-oxo-4-borabutenyl complex 4 was formed as a primary product through carboboration of the alkyne triple bond. The subsequent slow reaction of 4 at ambient temperature resulted in the formation of η3-boraallyl complex 5 and carbyne complex 6 in the ratio of 5:4. In all of these reactions, regioselective boration of the terminal carbon of alkynes was observed.
中文翻译：
经碱稳定的氢基（hydroborylene）的合成钨配合物及其与端炔为了给反应η 3 -Boraallyl配合
甲基（吡啶）钨配合物Cp *（CO）2 W（py）Me与硼烷-NHC（NHC = N-杂环卡宾; Me IMe，Me I i Pr）的反应（Me IMe = 1,3,4， 5- tetramethylimidazol -2-亚基，我本人我PR = 1,3-二异丙基-4,5-二甲基咪唑烷-2-亚基）加合物，得到NHC稳定氢基（hydroborylene）钨络合物的Cp *（CO）2 W（ħ ）（BH·NHC）（1a：NHC = Me IMe，1b：NHC = Me I iPr）呈深棕色晶体，高产，伴随有吡啶和甲烷的释放。X射线晶体结构分析表明，1b的W–B键被氢化配体桥接。的反应1a中，b在室温下与苯乙炔，得到NHC稳定η 3 -boraallyl络合物2a中，b，分别通过一种新型炔三键的硼氢化的：即，除了一个氢和一个borylene的。的反应1A与3-丁炔-2-酮也导致了三键的硼氢化，而不是C = O双键，得到η 3 -boraallyl复杂3。在1a的反应中与（三甲基甲硅烷基）乙炔一起，通过炔三键的碳硼化形成1-氧代-4-硼丁烯基络合物4作为主要产物。随后缓慢反应4在环境温度下导致η的形成3 -boraallyl复杂5和碳炔复杂6中的5：4的比例。在所有这些反应中，观察到炔烃的末端碳的区域选择性硼酸化。
更新日期：2017-11-20
中文翻译：
经碱稳定的氢基（hydroborylene）的合成钨配合物及其与端炔为了给反应η 3 -Boraallyl配合
甲基（吡啶）钨配合物Cp *（CO）2 W（py）Me与硼烷-NHC（NHC = N-杂环卡宾; Me IMe，Me I i Pr）的反应（Me IMe = 1,3,4， 5- tetramethylimidazol -2-亚基，我本人我PR = 1,3-二异丙基-4,5-二甲基咪唑烷-2-亚基）加合物，得到NHC稳定氢基（hydroborylene）钨络合物的Cp *（CO）2 W（ħ ）（BH·NHC）（1a：NHC = Me IMe，1b：NHC = Me I iPr）呈深棕色晶体，高产，伴随有吡啶和甲烷的释放。X射线晶体结构分析表明，1b的W–B键被氢化配体桥接。的反应1a中，b在室温下与苯乙炔，得到NHC稳定η 3 -boraallyl络合物2a中，b，分别通过一种新型炔三键的硼氢化的：即，除了一个氢和一个borylene的。的反应1A与3-丁炔-2-酮也导致了三键的硼氢化，而不是C = O双键，得到η 3 -boraallyl复杂3。在1a的反应中与（三甲基甲硅烷基）乙炔一起，通过炔三键的碳硼化形成1-氧代-4-硼丁烯基络合物4作为主要产物。随后缓慢反应4在环境温度下导致η的形成3 -boraallyl复杂5和碳炔复杂6中的5：4的比例。在所有这些反应中，观察到炔烃的末端碳的区域选择性硼酸化。
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