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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)ThCl4K2x(dme) (3; x = 0.5–2), which reacted with 2 equiv. of LiCH2SiMe3 or K[allylTMS] to afford the bis(hydrocarbyl) complexes [(XAd)Th(CH2SiMe3)2(THF)] (4) and [(XAd)Th(η3-allylTMS)2] {5; allylTMS = 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2a2b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(CH 2森达3 2(THF)]( 4)和[(XAD)钍(η 3 -烯丙基TMS 2 ] { 5 ; 烯丙基TMS= 1-(SiMe 3)C 3 H 4 }。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 1C 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2a45进行结晶学表征。
更新日期:2018-03-15
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