Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl 2 (OR) 2 complexes
Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl 2 (OR) 2 complexes
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二聚 Tl 2 (OR) 2 配合物的合成、表征和醇盐转移反应性
DOI：
10.1039/d0dt03917a
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发表时间：
2021
影响因子：
4
通讯作者：
Groysman, Stanislav
中科院分区：
文献类型：
--
作者：
Grass, Amanda;Kulathungage, Lakshani Wathsala;Wannipurage, Duleeka;Yousif, Maryam;Ward, Cassandra L.;Groysman, Stanislav
LiOCtBu2Ph与TlPF6反应形成二聚体Tl2(OCtBu2Ph)2配合物，这是一种罕见的同型醇酸铊配合物，具有正式的双坐标金属中心。对Tl2(OCtBu2Ph)2进行1H、13C NMR和x射线晶体学表征，发现存在两种异构体，它们的不同之处是烷氧配体的相互构象和中心Tl-O-Tl-O平面的平面度。Tl2(OCtBu2Ph)2是形成新旧[M(OCtBu2Ph)n]配合物（M = Cr, Fe, Cu, Zn）的方便前体，包括罕见的t形Zn(OCtBu2Ph)2（THF）配合物，这是以前使用更传统的LiOR/HOR前体无法合成的。[Ru(cymene)Cl2]2与Tl2(OCtBu2Ph)2反应生成钌（II）醇氧配合物。对于钌，烷氧化物的初始配位触发[OCtBu2Ph]的邻位h处的C-H活化，导致其双齿配位。除了Tl2(OCtBu2Ph)2外，还合成了相关的Tl2(OCtBu2(3,5- me2c6h3))2，并对其进行了表征，结果表明Tl2(OCtBu2(3,5- me2c6h3))2与铁和钌前体具有相似的反应活性。介绍了合成、结构和光谱表征。
Reaction of LiOCtBu2Ph with TlPF6 forms the dimeric Tl2(OCtBu2Ph)2 complex, a rare example of a homoleptic thallium alkoxide complex demonstrating formally two-coordinate metal centers. Characterization of Tl2(OCtBu2Ph)2 by 1H and 13C NMR spectroscopy and X-ray crystallography reveals the presence of two isomers differing by the mutual conformation of the alkoxide ligands, and by the planarity of the central Tl–O–Tl–O plane. Tl2(OCtBu2Ph)2 serves as a convenient precursor to the formation of old and new [M(OCtBu2Ph)n] complexes (M = Cr, Fe, Cu, Zn), including a rare example of T-shaped Zn(OCtBu2Ph)2(THF) complex, which could not be previously synthesized using more conventional LiOR/HOR precursors. The reaction of [Ru(cymene)Cl2]2 with Tl2(OCtBu2Ph)2 results in the formation of a ruthenium(II) alkoxide complex. For ruthenium, the initial coordination of the alkoxide triggers C–H activation at the ortho-H of [OCtBu2Ph] which results in its bidentate coordination. In addition to Tl2(OCtBu2Ph)2, related Tl2(OCtBu2(3,5-Me2C6H3))2 was also synthesized, characterized, and shown to exhibit similar reactivity with iron and ruthenium precursors. Synthetic, structural, and spectroscopic characterizations are presented.