Heterobimetallic-Mediated Dinitrogen Functionalization: N–C Bond Formation at Rhenium-Group 9 Diazenido Complexes
Heterobimetallic-Mediated Dinitrogen Functionalization: N–C Bond Formation at Rhenium-Group 9 Diazenido Complexes
复制标题
异双金属介导的二氮官能化：铼第 9 族二氮烯基配合物中 N−C 键的形成
DOI：
10.1021/acs.inorgchem.2c02463
复制
发表时间：
2022
影响因子：
4.6
通讯作者：
Arnold, John
中科院分区：
文献类型：
--
作者：
Ouellette, Erik T.;Magdalenski, Julian S.;Bergman, Robert G.;Arnold, John
报道了由Na[(η5-CP)Re(μ)]2与[μ(η4-CoD)]2发生盐消去反应而形成的9种稀土双氮杂多化合物(η5-CP)Re(μ-BDi)(MCL(η4-Cod))(1-M，M=Ir或Rh，Cp=环戊二烯，Bdi=N，MCL(η4-Cod)]2的合成和表征.此外，η(MCL(MCL)4-COD2)2与Re(MCl5-CP)Re(Bdi)Re(Bdi)(MCL(MCL(MCL)4-Cod))2发生盐消去反应，形成了9个含Re的双叠氮杂双金属物种(MCL 5-CP)Re(MCL(Bdi)Re(Bdi))(MCL(MCL(MCL 4-Cod))]2.我们发现这些试剂在Ar气氛下反应生成桥氢配合物([(η5-Cp)Re(μ-BDI)(μ-H)M(η4-COD)][(B(m-C6H3(CF3)2)4)])Re(μ-η_5：η_1-C_5H_4)(μ-H)M(COD4-η)(2-M)，它们在质子化时发生重排，形成可替代的桥氢化合物Re(3-M)。此外，我们展示了第一个通过1-M和三氟酸甲酯反应在异双金属二氮化合物上形成N-C键的例子，该反应生成了烷基化物种[(η5-CP)Re(μ-N(Me)N)(μ-Bdi)M(η4-CODe)][OTf](4-M，OTf=三氟甲磺酸)。光谱学研究、X射线结构分析和计算研究的结合被讨论，以帮助理解这些独特的异双金属配合物中的氮素活化模式。
We report the synthesis and characterization of rhenium-group 9 heterobimetallic diazenido species (η5-Cp)Re(μ-BDI)(μ-N2)M(η4-COD) (1-M, M = Ir or Rh, Cp = cyclopentadienide, BDI =N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate, COD = 1,5-cyclooctadiene), formed from salt elimination reactions between Na[(η5-Cp)Re(BDI)] and [MCl(η4-COD)]2. Additionally, we find that these same reagents react under an argon atmosphere to instead produce bridging hydride complexes (BDI)Re(μ-η5:η1-C5H4)(μ-H)M(η4-COD) (2-M), which undergo rearrangements upon protonation to form the alternative bridging hydrides [(η5-Cp)Re(μ-BDI)(μ-H)M(η4-COD)][(B(m-C6H3(CF3)2)4)] (3-M). Further, we demonstrate the first example of N–C bond formation at a heterobimetallic dinitrogen complex through reactions of1-Mand methyl triflate, which produces the alkylated species [(η5-Cp)Re(μ-N(Me)N)(μ-BDI)M(η4-COD)][OTf] (4-M, OTf = trifluoromethanesulfonate). A combination of spectroscopic studies, X-ray structural analysis, and computational investigations is discussed as an aid to understanding the modes of dinitrogen activation within these unique heterobimetallic complexes.