Phosphine ligands as protecting groups for 3d complexes in oxidation by O2
Phosphine ligands as protecting groups for 3d complexes in oxidation by O2
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膦配体作为 O2 氧化中 3d 配合物的保护基团
DOI：
10.1016/j.poly.2020.114609
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发表时间：
2020
期刊：
影响因子：
2.6
通讯作者：
Doerrer, Linda H.
中科院分区：
文献类型：
--
作者：
Brazeau, Sarah E.N.;Pope, Frances;Huang, Vincent L.;Anklin, Clemens;Rheingold, Arnold L.;Doerrer, Linda H.
设计了一系列杂配混合膦/醇盐 3d 配合物来评估 PPh3 作为保护基团，在 O2 暴露之前稳定金属配位球，但在 O2 存在下氧化解离，以便通过低配位金属中心轻松还原 O2。制备了 [(Ph3P)2M(OC4F9)2]（M = Fe (1)、Co (2)、Ni (3)、Zn (4)) 和 [(Ph3P)2M(pinF)]（M = Co (8)、Ni (9)、Zn (10)）形式的络合物，以及与非反应性供体 [(DME)Fe(OC4F9)2] (5) 相关的络合物和 [(Ph3PO)2M(OC4F9)2]（M = Fe (6)、Ni (7)）通过 UV-vis 和 NMR 光谱、元素分析和单晶 X 射线衍射对 1、3、6、7、8、9 和 10 进行了表征。3 的电子结构特别值得注意，在室温下具有 ~D4h 几何结构，在低温下具有 ~Tda 几何结构，由温度依赖性 UV-vis 和NMR (1H,31P) 光谱筛选配合物 (M = Fe, Co, Ni) 的 O2 反应性，以评估 PPh3 作为保护基团的功效。在 O2 与 1 发生反应后，分离出二聚体 [Fe2(μ2-O)(OPPh3)2(OC4F9)4] (13)，并按上述方法表征相关的 Fe 配合物 5 和 6，以生成能够具有两种化学计量的中间体。对苯二酚到苯醌的氧化酶和苯硫基苯甲醚 (PhSMe) 到甲基苯基亚砜的亚化学计量氧原子转移影响了 CoII 配合物中的 O2 反应性，因为反应性仅在含有较少空间位阻的 pinF 配合物中观察到，而在 NiII 配合物中，特定的氟化配体不是 O2 还原的因素，如 3 和 9 所示。类似的反应性也被分离和表征。
A series of heteroleptic mixed phosphine/alkoxide 3dcomplexes was designed to evaluate PPh3as a protecting group, stabilizing the metal coordination sphere prior to O2exposure, but oxidatively dissociating in the presence of O2to allow facile O2reduction by low coordinate metal centers. Complexes of the form [(Ph3P)2M(OC4F9)2] (M = Fe (1), Co (2), Ni (3), Zn (4)) and [(Ph3P)2M(pinF)] (M = Co (8), Ni (9), Zn (10) were prepared, along with related complexes with non-reactivel-donors, [(DME)Fe(OC4F9)2] (5) and [(Ph3PO)2M(OC4F9)2] (M = Fe (6), Ni (7)). Complexes were characterized by UV–vis and NMR spectroscopies, elemental analysis, and single-crystal X-ray diffraction for1,3,6,7,8,9, and10. The electronic structure of3is particularly notable, with ~D4hgeometry at room temperature and ~Tdat low temperature, as determined by temperature dependent UV–vis and NMR (1H,31P) spectroscopies. Complexes (M = Fe, Co, Ni) were screened for O2reactivity to assess the efficacy of PPh3as a protecting group. Dimeric [Fe2(μ2-O)(OPPh3)2(OC4F9)4] (13) was isolated after O2reactivity with1and characterized as described above. Related Fe complexes5and6were each combined with O2to generate intermediate species capable of both stoichiometric oxidase of hydroquinone to benzoquinone and sub-stoichiometric oxygen atom transfer of thioanisole (PhSMe) to methyl phenyl sulfoxide. Fluorinated alkoxide ligand choice influenced O2reactivity in CoIIcomplexes, as reactivity was only seen in the less sterically hindering pinF–containing complex8. In the NiIIcomplexes, on the other hand, the particular fluorinated ligand was not a factor in O2reduction, as3and9exhibited similar reactivity. Related dimeric compounds [Co2(pinF)2(THF)4)] (11) and [Zn2(pinF)2(THF)2)] (12) were also isolated and characterized.
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影响因子：
3.9
作者：
Cutsail, George E., III;Blaesi, Elizabeth J.;DeBeer, Serena
通讯作者：
DeBeer, Serena
影响因子：
62.1
作者：
Elwell CE;Gagnon NL;Neisen BD;Dhar D;Spaeth AD;Yee GM;Tolman WB
通讯作者：
Tolman WB
DOI：
--
发表时间：
1988
期刊：
影响因子：
--
作者：
C. J. Willis
通讯作者：
C. J. Willis
影响因子：
4.6
作者：
Smeets, Pieter J.;Woertink, Julia S.;Sels, Bert F.;Solomon, Edward I.;Schoonheydt, Robert A.
通讯作者：
Schoonheydt, Robert A.
影响因子：
62.1
作者：
Jasniewski AJ;Que L Jr
通讯作者：
Que L Jr