Synthesis and Reactivity of a Mono-Coordinated Triplet Bismuthinidene.

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI:10.1002/anie.202508250

Yannick Schulte, Timo Freese, Christoph Wölper, Jan Schulte, Gebhard Haberhauer, Stephan Schulz

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Abstract

The triplet bismuthinidene Ar*Bi (4) stabilized by a very bulky septiphenyl ligand (Ar* = 3,5-i-Pr₂-2,6-(2,6-Me₂-3,5-(2,6-i-Pr₂C₆H₃)₂-C₆H)-C₆H) was synthesized by dehydrogenation of in situ formed bismuth dihydride Ar*BiH₂ (3). Oxidative addition reactions of 4 with alkyl halides (MeI, EtBr, i-PrBr) yielded bismuthanes Ar*Bi(Me)I (5), Ar*Bi(Et)Br (6), and Ar*Bi(i-Pr)Br (7), which reacted with LiAlH₄ and LiAlD₄ to the thermally robust bismuth monohydrides Ar*Bi(R)H (R = Me 8, Et 10, i-Pr 12) and monodeuterides Ar*Bi(R)D (R = Me 9, Et 11, i-Pr 13). Ar*Bi(NMe₂)₂ 1 and Ar*BiH₂ 3 were characterized in situ by ¹H NMR spectroscopy and sc-XRD (1), whereas the other compounds were characterized by heteronuclear NMR (¹H/²H (D), ¹³C) and IR spectroscopy, elemental analysis (Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2, 4-7), as well as by UV-vis (4) and sc-XRD (Ar*-7, Ar*I, Ar*Li·Lit-Bu, Ar*H, 1, 2, 4, 12). Quantum chemical calculations revealed the triplet character of the bismuthinidine 4.

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单配位三态铋的合成及其反应性。

用原位生成的二氢化铋Ar*BiH2(3)脱氢法制备了体积庞大的七苯基配体（Ar* = 3,5-i- pr2 -2,6-(2,6- me2 -3,5-(2,6-i- pr2c6h3)2- c6h)- c6h）稳定的铋铋Ar*Bi(4)三重态。4与烷基卤化物（MeI, EtBr, I - prbr）氧化加成反应生成Ar*Bi(Me)I (5), Ar*Bi(Et)Br(6)和Ar*Bi(I - pr)Br(7)，与LiAlH4和LiAlD4反应生成热稳定的铋单氢化物Ar*Bi(R)H （R = Me 8, Et 10, I - pr 12）和单氘化物Ar*Bi(R)D （R = Me 9, Et 11, I - pr 13）。Ar*Bi(NMe2)21和Ar*BiH23通过1H NMR和sc-XRD(1)进行了原位表征，其他化合物通过异核NMR （1H / 2H (D), 13C）和IR光谱，元素分析（Ar*-2, Ar*-3, Ar*-5, Ar*-7, Ar*I, Ar*H, 2,4 -7）以及UV-vis(4)和sc-XRD （Ar*-7, Ar*I, Ar*Li∙Li - bu, Ar*H, 1,2,4,12）进行了表征。量子化学计算揭示了铋锑4的三重态性质。

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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Angewandte Chemie (International ed. in English)

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