Pelties Stefan, Maier Thomas, Herrmann Dirk, de Bruin Bas, Rebreyend Christophe, Gärtner Stefanie, Shenderovich Ilya G, Wolf Robert
Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 9747 AG, Groningen, Netherlands.
Chemistry. 2017 May 2;23(25):6094-6102. doi: 10.1002/chem.201603296. Epub 2016 Sep 21.
Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt ) {Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf) {Co(cod) }], reacts with P to afford [{K(thf)} {(BIAN)Co} (μ-η :η -P )] (2 a) in 61 % yield (isolated product). [{K(OEt )} {(BIAN)Co} (μ-η :η -P )] (2 b) and [K([18]crown-6)(MeCN)] [{(BIAN)Co} (μ-η :η -P )] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2 c). Oxidation of 2 a with [Cp Fe]BAr (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt ){(BIAN)Co} (μ-η :η -P )] (3 a) and [K(dme) ][{(BIAN)Co} (μ-η :η -P )] (3 b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co} (μ-η :η -P )] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp Fe]BAr . The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P units sandwiched between {(BIAN)Co} fragments.
尽管过渡金属多磷化物阴离子的化学性质已引起了广泛关注，但很少有研究报道直接由白磷合成此类物质。[K(OEt) {Co(BIAN)(cod)}]（1，BIAN = 1,2 - 双(2,6 - 二异丙基苯基亚氨基)苊，cod = 1,5 - 环辛二烯）可通过[K(thf) {Co(cod)}]的配体交换轻松制备，它与磷反应，以61%的产率（分离产物）生成[{K(thf)} {(BIAN)Co} (μ - η :η - P)]（2 a）。通过从乙醚和乙腈中重结晶2 a（对于2 c使用[18]冠醚 - 6）得到[{K(OEt)} {(BIAN)Co} (μ - η :η - P)]（2 b）和[K([18]冠醚 - 6)(MeCN)] [{(BIAN)Co} (μ - η :η - P)]（2 c）。用[Cp Fe]BAr（一当量）氧化2 a，随后从不同溶剂中重结晶产物，得到[K(OEt) {(BIAN)Co} (μ - η :η - P)]（3 a）和[K(dme) ][{(BIAN)Co} (μ - η :η - P)]（3 b；dme = 1,2 - 二甲氧基乙烷）。用两当量的[Cp Fe]BAr氧化2 a，以中等产率得到中性的[{(BIAN)Co} (μ - η :η - P)]（4）。通过核磁共振、电子顺磁共振（对于3 a）、紫外/可见光谱以及元素分析对新配合物进行了表征。X射线晶体学揭示的分子结构显示，平面环状或开链P单元夹在{(BIAN)Co}片段之间。
