Facile Addition of B–H and B–B Bonds to an Iron(IV) Nitride Complex
Facile Addition of B–H and B–B Bonds to an Iron(IV) Nitride Complex
复制标题
B-H 和 B-B 键轻松添加到氮化铁 (IV) 络合物中
DOI：
10.1021/acs.inorgchem.2c02931
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发表时间：
2022
影响因子：
4.6
通讯作者：
Smith, Jeremy M.
中科院分区：
文献类型：
--
作者：
Tran, Bao G.;Carta, Veronica;Pink, Maren;Caulton, Kenneth G.;Smith, Jeremy M.
铁（IV）络合物Ph B（iPr 2 Im）3Fe 3 N中的氮化物配体与硼氢化物反应得到Ph B（iPr 2 Im）3FeN（B）H（B= 9-BBN（1），Bpin（2）），与（Bpin）2反应得到Ph B（iPr 2 Im）3FeN（Bpin）2（3）。铁（II）硼酰氨基产品已全部进行了结构和光谱表征，证明容易插入B-H和B-B键的PhB（iPr 2 Im）3Fe N。密度泛函理论（DFT）计算表明，五重态（S= 2）的能量显着低于单重态（S= 0）和三重态（S= 1）的所有产品。与（Bpin）2的化学计量反应不产生单硼基化铁亚氨基物种PhB（iPr 2 Im）3FeN（Bpin）。DFT计算表明，这是因为PhB（iPr 2 Im）3FeN（Bpin）对于起始氮化铁（IV）和PhB（iPr 2 Im）3FeN（Bpin）2的反硝化是不稳定的。尝试在B-C键插入使用苯基和苄基频哪醇硼烷是不成功的，我们归因于不利的动力学。
The nitride ligand in the iron(IV) complex PhB(iPr2Im)3Fe≡N reacts with boron hydrides to afford PhB(iPr2Im)3FeN(B)H (B= 9-BBN (1), Bpin (2)) and with (Bpin)2to afford PhB(iPr2Im)3FeN(Bpin)2(3). The iron(II) borylamido products have all been structurally and spectroscopically characterized, demonstrating facile insertion into B–H and B–B bonds by PhB(iPr2Im)3Fe≡N. Density functional theory (DFT) calculations reveal that the quintet state (S= 2) is significantly lower in energy than the singlet (S= 0) and triplet (S= 1) states for all products. Stoichiometric reaction with (Bpin)2does not produce the mono-borylated iron imido species PhB(iPr2Im)3FeN(Bpin). DFT calculations suggest that this is because PhB(iPr2Im)3FeN(Bpin) is unstable toward disproportionation to the starting iron(IV) nitride and PhB(iPr2Im)3FeN(Bpin)2. Attempts at B–C bond insertion using phenyl- and benzyl-pinacol borane were unsuccessful, which we attribute to unfavorable kinetics.