Varied coordination geometries of an Alane/Tris(phosphine) ligand from its Reactions with Pt(0) and Au(I)

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2024-08-14 DOI:10.1016/j.poly.2024.117178

Samuel R. Lee, Brandy R. Adolph, Nattamai Bhuvanesh, Oleg V. Ozerov

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Abstract

Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand 1 (AlP₃) furnished an (AlP₃)Pt complex 2, which was determined to possess a Pt → Al interaction. Compound 2 reacted with CO to form the corresponding isolable adduct 3. Exposure of 2 to H₂ or HD in solution resulted in the observation of equilibrium binding which favors 2 at room temperature, and more strongly favored the adducts 2-H₂ and 2-HD at −80 °C. The presence of the Pt–H₂/HD moieties is supported by low temperature NMR determination of ¹J_PPt = 323 Hz (2-H₂) and ¹J_HD=34 Hz (2-HD), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of 1 with (tht)AuCl (tht = tetrahydrothiophene) generated compound 4 with loss of tht. An XRD study of 4 revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from 4 did not lead to a tripodal structure isoelectronic to 2, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound 5.

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从铂(0)和金(I)的反应看一种烷/三(膦)配体的不同配位几何结构

三(2-二异丙基膦-N-吡咯基)烷配体 1 (AlP3) 的反应生成了 (AlP3)Pt 复合物 2，经测定该复合物具有 Pt → Al 相互作用。化合物 2 与 CO 反应生成相应的可分离加合物 3。将 2 暴露于溶液中的 H2 或 HD 会导致平衡结合的观察结果，在室温下有利于 2，而在 -80 °C 下则更有利于加合物 2-H2 和 2-HD。1JPPt = 323 Hz（2-H2）和 1JHD=34 Hz（2-HD）的低温核磁共振测定结果证明了 Pt-H2/HD 分子的存在，这显然是具有三叉双锥几何形状的铂二氢配合物的第一个实例。1 与 (tht)AuCl（tht = 四氢噻吩）反应生成化合物 4，tht 丢失。对 4 的 XRD 研究表明，氯转移到了铝上，铝和金之间有很长的间隔，由三个膦臂配位。从 4 中萃取氯并没有产生与 2 等电子的三足结构，而是（根据溶液核磁共振证据）导致化合物 5 中的一个膦臂从金转移到了铝上。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.