Iron(I) in Negishi Cross-Coupling Reactions
Iron(I) in Negishi Cross-Coupling Reactions
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DOI：
10.1021/ja303250t
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发表时间：
2012-06-27
影响因子：
15
通讯作者：
Nunn, Joshua
中科院分区：
文献类型：
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作者：
Adams, Christopher J.;Bedford, Robin B.;Nunn, Joshua
在此，我们证明了 Fe(I) 在与芳基锌试剂的 Negishi 交叉偶联反应中的重要性以及催化活性 Fe(I) 中间体的分离。这些络合物，[FeX-(dpbz)(2)] [X = 4-甲苯基 (7)，Cl (8a)，Br (8b)； dpbz = 1,2-双(二苯基膦)苯]通过晶体学进行表征并测试了代表性反应的活性。该配合物是低自旋的，配体上没有显着的自旋密度。虽然复合物 8b 显示出与循环中间体一致的性能，但 7 似乎是非循环物质。
Herein we demonstrate both the importance of Fe(I) in Negishi cross-coupling reactions with arylzinc reagents and the isolation of catalytically competent Fe(I) intermediates. These complexes, [FeX-(dpbz)(2)] [X = 4-tolyl (7), Cl (8a), Br (8b); dpbz = 1,2-bis(diphenylphosphino)benzene], were characterized by crystallography and tested for activity in representative reactions. The complexes are low-spin with no significant spin density on the ligands. While complex 8b shows performance consistent with an on-cycle intermediate, it seems that 7 is an off-cycle species.