Characterization of Structurally Unusual Diiron NxHy Complexes
Characterization of Structurally Unusual Diiron NxHy Complexes
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DOI：
10.1021/ja903967z
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发表时间：
2009-08-05
影响因子：
15
通讯作者：
Peters, Jonas C.
中科院分区：
文献类型：
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作者：
Saouma, Caroline T.;Mueller, Peter;Peters, Jonas C.
以三（膦）硼酸盐（[PhB（CH_2 PR_2）（3）] = [PhBP_3R]）为稳定剂，合成了一系列具有NxHy桥连结构的二铁配合物。通过[PhBP 3R]Fe-Me（R = Ph或环己基甲基）的肼活化导致二铁Fe-2（μ-η（1）：η（1）-N2 H4）（μ-η（2）：η（2）-N2 H2）络合物，其特征在于桥接肼和酰肼基配体。{[PhBP_（23）CHCy]Fe}（2）（μ-η（1）：η（1）-N_2H_4）（μ-η（2）：η（2）-N_2H_2）在22 ℃下的热分解导致结构上不寻常的{[PhBP_（23）CHCy]Fe}（2）（μ-η（1）：η（1）-N_2H_2）（μ-NH_2）（2）络合物，其特征在于桥接HN=NH和NH_2-配体。这与{[PhBP 3 Ph]Fe}（2）（μ-η（1）：η（1）-N2 H2）（μ-η（2）：η（2）-N2 H2）形成对比，根据条件，其可以被化学氧化以产生{[PhBP 3 Ph]Fe}（2）（μ-η（1）：η（1）-N2 H2）（μ-η（2）：η（2）-N2 H2）或{[PhBP 3 Ph]Fe}（2）（μ-NH）（2）。前一种产物是唯一已知的含有桥连N2 H2配体的复合物，其氧化极限状态为（HN=NH vs HN-NH 2-）。后一种产物构成二铁Fe-2（μ-NH）（2）菱形核的第一个实例。
A series of fascinating diiron complexes featuring bridging NxHy ligands stabilized by tris(phosphine)borate ([PhB(CH2PR2)(3)] = [PhBP3R]) ligands have been characterized. Hydrazine activation by [PhBP3R]Fe-Me (R = Ph or cyclohexylmethyl) leads to diiron Fe-2(mu-eta(1):eta(1)-N2H4) (mu-eta(2):eta(2)-N2H2) complexes featuring both bridging hydrazine and hydrazido ligands. Thermolysis of {[PhBP23CHCy]Fe}(2)(mu-eta(1):eta(1)-N2H4) (mu-eta(2):eta(2)-N2H2) at 22 degrees C leads to a structurally unusual {[PhBP2CHCy]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-NH2)(2) complex featuring bridging HN=NH and NH2- ligands. This contrasts with {[PhBP3Ph]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-eta(2):eta(2)-N2H2), which can be chemically oxidized to produce either {[PhBP3Ph]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-eta(2):eta(2)-N2H2) or {[PhBP3Ph]Fe}(2)(mu-NH)(2), depending on the conditions. The former product is the only known complex to contain bridging N2H2 ligands in each of their limiting states of oxidation (HN=NH vs HN-NH2-). The latter product constitutes the first example of a diiron Fe-2(mu-NH)(2) diamond-shaped core.