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Molybdenum Disubstituted Alkylidene Complexes
Organometallics ( IF 2.5 ) Pub Date : 2020-02-24 , DOI: 10.1021/acs.organomet.9b00812
Jordan W. Taylor 1 , Richard R. Schrock 1 , Charlene Tsay 1
Affiliation  

Through relatively straightforward techniques that begin with Mo(NAr)(CH-t-Bu)[OCMe(CF3)2]2 (Ar = 2,6-i-Pr2C6H3), we have prepared Mo(NAr)(CMePh)(OMesityl)2, [Mo(NAr)(CMePh)(OC6F5)2]2, Mo(NAr)(CMePh)(OC6F5)2(MeCN), Mo(NAr)(CMePh)(OC6F5)2(bipyridyl), Mo(NAr)(CMePh)(Cl)2(bipyridyl), Mo(NAr)(CMePh)(Cl)(OHMT)(MeCN) (OHMT = O-2,6-(2,4,6-Me3C6H2)2C6H3), and Mo(NAr)(CMePh)(Pyrrolide)(OHMT). X-ray studies reveal that in five compounds the alkylidene isomer (A) is that in which the phenyl group in the alkylidene points toward the imido nitrogen. In Mo(NAr)(CMePh)(OC6F5)2(MeCN) the isomer in which the methyl group points toward the imido nitrogen (isomer B) has cocrystallized with isomer A (12%). In two 14e compounds that contain isomer A, the Mo═C–C angles differ by 30–36°, consistent with a Mo. . .C–Hβ agostic interaction. Several of the complexes reported here react readily with ethylene, 1-decene, or cyclooctene to give the expected products, thus confirming their viability as initiators or intermediates in metathesis reactions.

中文翻译:

钼二取代亚烷基络合物

通过以Mo(NAr)(CH- t -Bu)[OCMe(CF 32 ] 2(Ar = 2,6- i -Pr 2 C 6 H 3)开头的相对简单的技术,我们制备了Mo(NAr )(CMePh)(OMesityl)2,[Mo(NAr)(CMePh)(OC 6 F 52 ] 2,Mo(NAr)(CMePh)(OC 6 F 52(MeCN),Mo(NAr)( CMePh)(OC 6 F 52(联吡啶),Mo(NAr)(CMePh)(Cl)2(联吡啶基),Mo(NAr)(CMePh)(Cl)(OHMT)(MeCN)(OHMT = O-2,6-(2,4,6-Me 3 C 6 H 22 C 6 H 3),和Mo(NAr)(CMePh)(吡咯化物)(OHMT)。X射线研究表明,在五种化合物中,亚烷基异构体(A)是亚烷基中的苯基指向亚氨基氮的异构体。在Mo(NAr)(CMePh)(OC 6 F 52(MeCN)中,甲基指向亚氨基氮的异构体(异构体B)与异构体A(12%)共结晶。在两个包含异构体A的14e化合物中,Mo═C–C角相差30–36°,与Mo一致。。。C-H β抓氢键。此处报道的几种配合物很容易与乙烯,1-癸烯或环辛烯反应,得到所需的产物,从而确认了它们在复分解反应中作为引发剂或中间体的可行性。
更新日期:2020-02-24
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