Thorium(iv) alkyl and allyl complexes of a rigid NON-donor pincer ligand with flanking 1-adamantyl substituents†,Dalton Transactions

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Thorium(iv) alkyl and allyl complexes of a rigid NON-donor pincer ligand with flanking 1-adamantyl substituents†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-03-15 00:00:00 , DOI: 10.1039/c8dt00421h
Nicholas R. Andreychuk _{1,

2,

3,

4} , Tara Dickie _{1,

2,

3,

4} , David J. H. Emslie _{1,

2,

3,

4} , Hilary A. Jenkins _{1,

2,

3,

4}

Affiliation

Palladium-catalyzed coupling of 1-adamantylamine (2 equiv.) with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene afforded the proligand 4,5-bis(1-adamantylamino)-2,7-di-tert-butyl-9,9-dimethylxanthene, H₂[XAd] (1), which upon deprotonation with excess KH or KCH₂Ph in THF or dme generated [{K(THF)₃}₂(XAd)] (2a) and [K₂(XAd)(dme)] (2b). Subsequent reaction of in situ generated 2a or 2b with [ThCl₄(dme)₂] yielded [(XAd)ThCl₄K₂]·x(dme) (3; x = 0.5–2), which reacted with 2 equiv. of LiCH₂SiMe₃ or K[allyl^TMS] to afford the bis(hydrocarbyl) complexes [(XAd)Th(CH₂SiMe₃)₂(THF)] (4) and [(XAd)Th(η³-allyl^TMS)₂] {5; allyl^TMS = 1-(SiMe₃)C₃H₄}. Dialkyl complex 4 was stable at 80 °C for at least 2.5 hours, but decomposed over 4.5 hours at 110 °C. Diallyl complex 5 was stable for hours at 85 °C, and suffered less than 5% decomposition after 10 minutes at 155 °C. At room temperature, averaging of the syn and anti protons of the allyl CH₂ groups of 5 occurred on the NMR timescale, as a consequence of rapid π–σ–π hapticity changes. Additionally, low temperature ¹H and ¹³C NMR spectroscopy indicates that 5 exists as a rapidly exchanging mixture of two isomers with C₁ and C₂ symmetry. Compounds 2a, 4 and 5 were crystallographically characterized.

中文翻译：

刚性的非供体钳形配体的侧接1-金刚烷基取代基的（iv）烷基和烯丙基配合物†

1-金刚烷胺（2当量）与4,5-二溴-2,7-二叔丁基-9,9-二甲基x吨的钯催化偶联提供了配体4,5-双（1-金刚烷氨基）-2 ，7-二叔丁基-9,9-二甲基x吨，H ₂ [XAd]（1），在过量的KH或KCH ₂ Ph在THF或dme中脱质子化后生成[{K（THF）₃ } ₂（XAd ）]（2a）和[K ₂（XAd）（dme）]（2b）。随后原位生成的2a或2b与[ThCl ₄（dme）₂ ]反应，生成[（XAd）ThCl ₄ K₂ ]· x（dme）（ 3 ; x = 0.5–2），与2当量反应。的LiCH的₂森达₃或K [烯丙基^TMS ]，得到双（烃基）配合物[（XAD）的Th（CH₂森达₃）₂（THF）]（ 4）和[（XAD）钍（η³ -烯丙基^TMS）₂ ] { 5 ; 烯丙基^TMS＝ 1-（SiMe₃）C₃ H₄ }。二烷基络合物4在80℃下稳定至少2.5小时，但在110℃下在4.5小时内分解。二烯丙基复合物5在85℃下稳定数小时，并且在155℃下10分钟后分解少于5％。在室温下，由于π-σ-π迅速的触觉变化，在NMR时标上出现了5个烯丙基CH ₂基团的合成和反质子的平均值。另外，低温¹ H和¹³ C NMR光谱表明5以具有C ₁和C ₂对称性的两种异构体的快速交换混合物形式存在。对化合物2a，4和5进行结晶学表征。

更新日期：2018-03-15

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