Scholarlink

<p>Hydroboration of carbonyl compounds has proven a pivotal route to access alcohols and other C1 moieties in recent years. Despite this, iron-based catalyst systems are somewhat limited with very little mechanistic understanding of these systems developed. Here we show that an iron metalloborane complex [{(<sup><i>i</i>Pr</sup>DPB<sup>Ph</sup>)Fe}<sub>2</sub>(μ−1,2-N<sub>2</sub>)] (<b>A</b>) is an efficient pre-catalyst for hydroboration of ketones, cyclic esters and CO<sub>2</sub> with mild conditions. Mechanistic insights reveal a previously unreported direct iron(0)-mediated ligand-to-ligand hydride transfer (LLHT) process is in operation with B–H bond breaking being rate determining, indicating the importance of mechanistic studies on well-known transformations. An iron(I)-benzophenone ketyl radical with a unique <i>S</i> = 1 antiferromagnetic ground state has been isolated and fully characterized.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Iron-borane catalyzed carbonyl hydroboration and isolation of an iron(I)-ketyl radical

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年2月19日

查看全文
  • Laura A. Grose,
  • Ryan J. Schwamm,
  • Adam Brookfield,
  • David Robinson,
  • Darren Willcox

摘要

Hydroboration of carbonyl compounds has proven a pivotal route to access alcohols and other C1 moieties in recent years. Despite this, iron-based catalyst systems are somewhat limited with very little mechanistic understanding of these systems developed. Here we show that an iron metalloborane complex [{(iPrDPBPh)Fe}2(μ−1,2-N2)] (A) is an efficient pre-catalyst for hydroboration of ketones, cyclic esters and CO2 with mild conditions. Mechanistic insights reveal a previously unreported direct iron(0)-mediated ligand-to-ligand hydride transfer (LLHT) process is in operation with B–H bond breaking being rate determining, indicating the importance of mechanistic studies on well-known transformations. An iron(I)-benzophenone ketyl radical with a unique S = 1 antiferromagnetic ground state has been isolated and fully characterized.