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Synthetic and Computational Studies on the Thermal and Photochemical Reactions of [NPN]TaMe3 (NPN = PhP(CH2SiMe2NPh)2) and [MesNPN]TaMe3 (MesNPN = PhP(CH2SiMe2N(2,4,6-Me3C6H2))2)
Organometallics ( IF 2.8 ) Pub Date : 2017-09-07 00:00:00 , DOI: 10.1021/acs.organomet.7b00487
Aleksandra Zydor 1 , Richard J. Burford 1 , Michael D. Fryzuk 1
Affiliation  

The thermolysis of [PhP(CH2SiMe2NPh)2]TaMe3 leads to the elimination of methane and the formation of cyclometalated derivative [PhP(CH2SiMe2NPh)(CH2SiMe2N-o-C6H4)]TaMe2, which was characterized by NMR spectroscopy and single crystal X-ray analysis. Computational studies confirm the expected four-membered transition state involving an ortho-N-phenyl-C–H bond and a Ta-methyl unit. The photolysis of [PhP(CH2SiMe2NPh)2]TaMe3 takes a different course; loss of methane also occurs but results in the formation the methylidene complex, [PhP(CH2SiMe2NPh)2]Ta═CH2(Me), which was characterized by NMR spectroscopy. Attempts to block the cyclometalation process by replacement of the N-phenyl substituent with N-Mesityl (Mesityl = 2,4,6-Me3C6H2) is also reported. With this bulkier ancillary ligand, the reactions are more complicated with multiple products being observed in an overall slow process. The reactions of the trimethyl, the cyclometalated product and the methylidene with H2 were also investigated and found to exhibit different rates of hydrogenolysis. This has implications for some of the steps in the reaction of [PhP(CH2SiMe2NPh)2]TaMe3 with H2 to generate dinuclear tetrahydride ([PhP(CH2SiMe2NPh)2]Ta)2(μ-H)4.

中文翻译:

[NPN] TaMe 3(NPN = PhP(CH 2 SiMe 2 NPh)2)和[ Mes NPN] TaMe 3Mes NPN = PhP(CH 2 SiMe 2 N(2, 4,6-Me 3 C 6 H 2))2

[PhP(CH 2 SiMe 2 NPh)2 ] TaMe 3的热分解导致甲烷的消除和环金属化衍生物[PhP(CH 2 SiMe 2 NPh)(CH 2 SiMe 2 N- o- C 6 H 4)的形成)] TaMe 2,通过NMR光谱和单晶X射线分析表征。计算研究证实涉及一个预期的四元过渡态- ñ -苯基-C-H键和钽-甲基单元。[PhP(CH 2 SiMe 2 NPh)2的光解] TaMe 3采取不同的路线;甲烷的损失也会发生,但导致形成的亚甲基络合物,[PHP(CH 2森达2 NPH)2 ]Ta═CH 2(ME),其特点是NMR光谱。还报道了试图通过用N- Mesityl(Mesityl = 2,4,6-Me 3 C 6 H 2)代替N-苯基取代基来阻断环金属化过程的尝试。使用这种较大的辅助配体,在整个缓慢的过程中观察到多种产物,反应变得更加复杂。三甲基,环金属化产物和亚甲基与H 2的反应还对它们进行了研究,发现它们表现出不同的氢解速率。这对[PhP(CH 2 SiMe 2 NPh)2 ] TaMe 3与H 2反应生成双核四氢化物([PhP(CH 2 SiMe 2 NPh)2 ] Ta)2(μ- H)4
更新日期:2017-09-07
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