Synthesis of Molybdenum(VI) Tritylimido Alkylidene Complexes

Synthesis of Molybdenum(VI) Tritylimido Alkylidene Complexes
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钼(VI)三苯甲基亚氨基亚烷基配合物的合成

DOI:
10.1021/acs.organomet.2c00189
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发表时间:
2022
期刊:
影响因子:
2.8
通讯作者:
Carta, Veronica
Carta, Veronica
中科院分区:
化学2区
文献类型:
--
作者:
Paul, Bhaskar;Schrock, Richard R.;Carta, Veronica

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在二甲氧基乙烷存在下,Mo(NCPh3)2(CH2CMe2Ph)2(CH2CMe2Ph)2与3当量的三氟甲酸反应,以46%的产率合成了Mo(NCPh3)(CHCMe2Ph)(OTf)2(DME)(1)。合成的其他三胺配合物包括Mo(NCPh3)(CHCMe2Ph)[OC(CF3)3]2(2),Mo(NCPh3)(CHCMe2Ph)(OSiPh3)2(3),Mo(NCPh3)(CHCMe2Ph)(η5-Me2Pr)(η1-Me2Pyr)(4;Me2Pyr=2,5-二甲基吡咯烷),Mo(NCPh3)(CH2CH2)(OTf)2(DME)(5),Mo(NCPh3)(OSiPh3)2Cl2(THF)(6),和[(Ph3SiO)2(NCPh3)]Mo 2(μ-O)(μ-Cl)2(7)。对2、4、5、6和7进行了单晶X射线衍射研究。这些结果表明,tritylimido是一种强大的、空间要求较高的烷基亚胺配体,补充了空间需求较少的t-丁基亚胺和1-金刚烷基亚胺配体。
Mo(NCPh3)(CHCMe2Ph)(OTf)2(DME) (1) can be prepared in 46% yield through addition of 3 equiv of triflic acid to Mo(NCPh3)2(CH2CMe2Ph)2in the presence of dimethoxyethane. Other tritylimido complexes that were prepared include Mo(NCPh3)(CHCMe2Ph)[OC(CF3)3]2(2), Mo(NCPh3)(CHCMe2Ph)(OSiPh3)2(3), Mo(NCPh3)(CHCMe2Ph)(η5-Me2Pyr)(η1-Me2Pyr) (4; Me2Pyr = 2,5-dimethylpyrrolide), Mo(NCPh3)(CH2CH2)(OTf)2(DME) (5), Mo(NCPh3)(OSiPh3)2Cl2(THF) (6), and [(Ph3SiO)2(NCPh3)Mo]2(μ-O)(μ-Cl)2(7). Single crystal X-ray diffraction studies were carried out for2,4,5,6, and7. These results demonstrate that tritylimido is a robust, sterically demanding alkylimido ligand that complements less sterically demandingt-butylimido and 1-adamantylimido ligands.
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