A base-free terminal thorium phosphinidene metallocene and its reactivity toward selected organic molecules
A base-free terminal thorium phosphinidene metallocene and its reactivity toward selected organic molecules
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无碱末端钍次膦茂金属及其对选定有机分子的反应性
DOI：
10.1039/c9dt00012g
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发表时间：
2019
影响因子：
4
通讯作者：
Walter Marc D
中科院分区：
文献类型：
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作者：
Zhang Congcong;Hou Guohua;Zi Guofu;Walter Marc D
[η5-1，2，4-(Me3C)3C5H2]2ThP-2，4，6-tBu3C6H2(2)可从二氯化钍配合物[η5-1，2，4-(Me3C)3C5H2]2ThCl2(1)与2当量V.2，4，6-(Me_3C)_3C_6H_2PHK在四氢呋喃中。考察了2在二硒化物、膦、亚胺、酮、膦氧化物、噻唑、咪唑类、胺类等有机小分子的活化中的反应活性。例如，当配合物2用Ph2Se2处理时，亚膦被取代，生成二硒化合物[η5-1，2，4-(Me3C)3C5H2]2th(Seph)2(3)。此外，2与2，4，6-κ-C-1，2-(Me3C)2-4-(CH2CMe2)C5H2]Th(PH-2，4，6-iPr3C6H2)，2，4，6-iPr3C6HPH2，PhPh2，(对甲苯基)2CNH，1-吲哚，环己酮，Me3PO，噻唑，1-甲基咪唑和对甲基苯胺作用时，E-H(E=P，N，C)键被激活，得到磷酸盐配合物[η5-1，2，4-(Me3C)3C5H2][η5，PhPh2，金属杂环[η5-1，2，2，4-(Me3C)3C5H2]2Th(Me3C)3C5H2)(5)，亚胺基膦配合物[η5-1，2，4-(Me3C)3C5H2]2Th(PH-2，4，6-tBu3C6H2)[NC(p-tolyl)2](6)，磷烯醇基化合物[η5-1，2，4-(Me3C)3C5H2]2Th(PH-2，4，6-tBu3C6H2)(κ-O-1-OC9H7)(7)，烯醇基配合物[η5-1，2，4-(Me3C)3C5H2][η5，κ-C-1，2-(Me3C)2-4-(CH2CMe2)C5H2]Th(κ-O-1-OC6H9)(8)，烷基配合物[[η5-1，2，4-(Me3C)3C5H2]2Th(PH-2，4，6-tBu3C6H2)(C3H2NS)5-1，2，4-(Me3C)3C5H2][η5，η-C-1，2-(Me3C)2-4-(CH2CMe2)C5H2]Th(κ-O，C-OPMe2CH2)(9)，膦基噻唑络合物η(10)，双咪唑络合物[η5-1，2，4-(Me3C)3C5H2]2[2-(1-MeC3H2)]2(11)和亚胺配合物[η5-1，2，4-(Me3C)3C5H2]2ThN(p-甲苯基)(12)。用多种光谱技术对新化合物3-11进行了表征，并用X-射线衍射法进一步确定了化合物3-6、8-9和11的固态分子结构。
The stable base-free terminal phosphinidene thorium metallocene, [η5-1,2,4-(Me3C)3C5H2]2ThP-2,4,6-tBu3C6H2 (2), can be isolated from the reaction of the thorium dichloride complex [η5-1,2,4-(Me3C)3C5H2]2ThCl2 (1) with 2 equiv. of 2,4,6-(Me3C)3C6H2PHK in THF. The reactivity of 2 in the activation of various small organic molecules such as diselenides, phosphines, imines, ketones, phosphine oxides, thiazole, imidazole derivatives and amines was explored. For example, when complex 2 is treated with Ph2Se2, the phosphinidene is replaced, yielding diselenido compound [η5-1,2,4-(Me3C)3C5H2]2Th(SePh)2 (3). Moreover, E–H (E = P, N, C) bond activation occurs on exposure of 2 to 2,4,6-iPr3C6H2PH2, PhPH2, (p-tolyl)2CNH, 1-indanone, cyclohexanone, Me3PO, thiazole, 1-methylimidazole and p-toluidine, resulting in the phosphido complex [η5-1,2,4-(Me3C)3C5H2][η5,κ-C-1,2-(Me3C)2-4-(CH2CMe2)C5H2]Th(PH-2,4,6-iPr3C6H2) (4), the metallaheterocycle [η5-1,2,4-(Me3C)3C5H2]2Th(η2-P2Ph2) (5), the iminato phosphido complex [η5-1,2,4-(Me3C)3C5H2]2Th(PH-2,4,6-tBu3C6H2)[NC(p-tolyl)2] (6), the phosphido enolyl compound [η5-1,2,4-(Me3C)3C5H2]2Th(PH-2,4,6-tBu3C6H2)(κ-O-1-OC9H7) (7), the enolyl complex [η5-1,2,4-(Me3C)3C5H2][η5,κ-C-1,2-(Me3C)2-4-(CH2CMe2)C5H2]Th(κ-O-1-OC6H9) (8), the alkyl complex [η5-1,2,4-(Me3C)3C5H2][η5,κ-C-1,2-(Me3C)2-4-(CH2CMe2)C5H2]Th(κ-O,C-OPMe2CH2) (9), the phosphido thiazolyl complex [η5-1,2,4-(Me3C)3C5H2]2Th(PH-2,4,6-tBu3C6H2)(C3H2NS) (10), the bis-imidazolyl complex [η5-1,2,4-(Me3C)3C5H2]2Th[2-(1-MeC3H2N2)]2 (11), and the imido complex [η5-1,2,4-(Me3C)3C5H2]2ThN(p-tolyl) (12), respectively. Several spectroscopic techniques were employed for the characterisation of the new complexes 3–11, and in addition the solid-state molecular structures of compounds 3–6, 8–9 and 11 were further confirmed by X-ray diffraction analyses.