Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1).
Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1).
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均配二磷环丁二烯配合物 [M(η(4)-P2C2R2)2]x-（M = Fe, Co；x = 0, 1）。
DOI：
10.1002/chem.201001913
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
K. Lammertsma
中科院分区：
文献类型：
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作者：
Robert Wolf;Robert Wolf;A. Ehlers;Marat M. Khusniyarov;F. Hartl;F. Hartl;B. Bruin;G. J. Long;F. Grandjean;Falko M. Schappacher;R. Pöttgen;J. Slootweg;M. Lutz;A. Spek;K. Lammertsma
报道了一系列含二磷酸环丁二烯配体的同色夹层配合物的制备和综合表征。化合物[K ([18] crown-6)(四氢呋喃)(2)](Fe(η(4)C - P (2) (2) tBu (2) (2)] (K1), [K ([18] crown-6)(四氢呋喃)(2)][有限公司(η(4)C - P (2) (2) tBu (2) (2)] (K2)和[K ([18] crown-6)(四氢呋喃)(2)][有限公司(η(4)C - P(2)(2)广告(2))(2)](K3,广告= adamantyl)得到的反应[K ([18] crown-6)(四氢呋喃)(2)][M(η(4)- C (14) H (10)) (2)] (M =铁、Co) tBuC(三键)P(1、2),或与AdC(三键)P(3)。用[Cp(2)Fe]PF(6)氧化1和2得到中性夹层[M(η(4)-P(2)C(2)tBu(2))(2)] （4: M = Fe 5: M = Co）。循环伏安法和光谱电化学分析表明，[M(η(4)- p (2)C(2)tBu(2))(2)](-)/[M(η(4)- p (2)C(2)tBu(2))(2)]两个基团分别可以通过单电子氧化和还原可逆地相互转化。配合物1-5通过多核NMR、EPR（1和5）、UV/Vis和Mössbauer光谱（1和4）、质谱（4和5）和微量分析（1-3）进行了表征。用x射线晶体学测定了1 ~ 5的分子结构。这五种配合物基本上都是D（2d）对称结构，这表明两个1,3-二磷酸环丁二烯环在交错方向上。密度泛函理论计算揭示了共价金属-配体π键在1-5中的重要性。讨论了金属离子可能的氧化态分配。
The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and Mössbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed.