1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate | 67292-48-2

• 英文名称: 1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate
• 英文别名: 1,1'-bis(diphenylphsphino)cobaltocenium hexafluorophosphate
• CAS: 67292-48-2
• 化学式: C₃₄H₂₈CoP₂*F₆P
• 分子量: 702.501
• InChiKey: BUVQUMACVJAHMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  五羰基溴铼(I) 、 1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate 以 二乙二醇二甲醚 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Use of a Redox-Active Ligand to Reversibly Alter Metal Carbonyl Electrophilicity

  摘要：

  The chelating ligand, 1,1'-bis(diphenylphosphino)cobaltocene (dppc) is used as an electrochemically tunable ligand for altering electrophilicity of the carbonyl carbon in metal carbonyl complexes. The Re carbonyl complexes [Re(CO)(4-n)(CH3CN)(n)dppc](2+/+), n = 0 (cis), 1 (fac), 2 (cis,cis), and [fac-Re(CO)(3)(NCO)dppc](+/0) were prepared and characterized in both stales of charge indicated. Single crystal X-ray crystallography was performed for both states of charge of [Re(CO)(4)dppc](2+/+ with the oxidized and reduced forms crystallizing in the monoclinic space groups C2/c and P2?1/c, respectively; The most pronounced structural difference between the two forms is the Cp(centroid)-Co distance, which is 0.09 Angstrom longer for the reduced form. Cyclic voltammetry shows that E(1/2) for the Co(III)/Co(II) couple is 200-400 mV more positive for coordinated dppc than for the free ligand. For each CO substituted, E(1/2) becomes similar to 100 or 200 mV more negative for substitution by CH3CN or NCO-, respectively. Solution IR spectroscopy shows that v(CO) for the oxidized form of each species is typically similar to 15 cm(-1) higher than for the reduced form, but the dumber and relative intensities of the carbonyl absorptions are the same. In every redox pair the oxidized species has higher reactivity with respect to nucleophilic attack at the carbonyl carbon. In CH3CN at 25.0 degrees C, [fac-Re(CO)(3)- (CH3CN)dppc](+2) reacts with amine N-oxides (CH3)(3)NO, N-methylmorpholine N-oxide, and (CH3)(2)(C6H5)NO similar to 200 times faster than [fac-Re(CO)(3)(CH3CN)dppc](+) to form [cis,cis-Re(CO)(2)(CH3CN)(2)dppc](+2/+), while [cis-Re(CO)(4)dppc](+2) reacts with N-3(-) 5400 times faster than [cis-Re(CO)(4)dppc](+) to form [fac-Re(CO)(3)(NCO)dppc](+/0), with Delta Delta H double dagger = 3-4 kcal/mol in both cases. The ionic strength and dielectric strength dependence of the reactivity of [Re(CO)(4)dppc](+2/+) toward N-3(-) were assayed to investigate electrostatic contributions to the attenuation of reactivity of [Re(CO)(4)dppc](+2/+) toward N-3(-) caused by reduction of the dppc ligand.

  DOI：

  10.1021/ja00093a023
• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 1,1'-bis(diphenylphosphino)cobaltocene 在 air 作用下， 以 四氢呋喃 、 水 、 溶剂黄146 为溶剂， 生成 1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate
  参考文献：
  名称：

  1,1'-双（二苯基膦基）二茂铁和1,1'-双（二苯基膦基）钴茂簇衍生物的新型行为和反应活性

  摘要：

  团簇[Ru 6 C（CO）16 {Fe（C 5 H 4 P（Ph）2 } 2）] 2和[Ru 6 C（CO）15 { μ -Fe（C 5 H 4 P（Ph）2）2 }] 3是由母体簇[Ru 6 C（CO）17 ] 1与1,1'-双（二苯基膦基）二茂铁（dppf）在THF中的反应合成的。相关化合物[Ru 5 C（CO）13 { μ -Fe（C 5 H 4P（Ph）2）2 }] 4是在更强的条件下从2和3产生的。簇3和簇4都已通过单晶X射线分析进行了结构表征。在图3中，dppf配体以邻位形式进行配位，簇核心为高度扭曲的八面体。在第4版中，保留了邻位模式，但dppf配体与方基金字塔的相邻基础原子配位。CD 2 Cl 2中3和4的31 P-NMR光谱在各种温度下显示出高度的立体化学非刚性行为。在一定温度范围内的磁化率测量结果表明3在所有温度下都是顺磁性的。的电化学研究1，3，4和相关的[Ru 6 C（CO）15

  DOI：

  10.1016/s0022-328x(98)00565-8

文献信息

• Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds
  作者：Kyle D. Reichl、Chelsea L. Mandell、Owen D. Henn、William G. Dougherty、W. Scott Kassel、Chip Nataro

  DOI：10.1016/j.jorganchem.2011.09.004

  日期：2011.12

  phosphinothioyl ([dppcS2][PF6], [dcpcS2][PF6], [dippcS2][PF6], [1-dtbpcS][PF6], and 1,1′-bis(dicyclohexylphosphinothioyl)ferrocene) and phosphinoselenoyl derivatives ([dppcSe2][PF6], [dcpcSe2][PF6], [dippcSe2][PF6], [1-dtbpcSe][PF6], and 1,1′-bis(dicyclohexylphosphinoselenoyl)ferrocene) were prepared and characterized, and the structures of eight of these compounds were determined. The electrochemistry of these

  1,1'-双（二苯基膦基）六氟磷酸钴铈（[dppc] [PF 6 ]），1,1'-双（二环己基膦基）六氟磷酸钴铯（[dcpc] [PF 6 ]），1,1'-的电化学用二氯甲烷和四丁基铵在二氯甲烷中检测了双（二异丙基膦基）六氟磷酸钴铈（[dippc] [PF 6 ]）和1-（二叔丁基膦基）六氟磷酸钴铈（[1-dtbpc] [PF 6 ]）。六氟磷酸盐作为支持电解质。在更负的电势下观察到可逆的还原波，然后是不可逆的波。十个新的膦硫硫基（[dppcS 2 ] [PF 6 ]，[dcpcS 2 ] [PF 6 ]，[dippcS 2] [PF 6 ]，[1-dtbpcS] [PF 6 ]和1,1'-双（二环己基膦硫基硫基）二茂铁）和膦硒烯酰基衍生物（[dppcSe 2 ] [PF 6 ]，[dcpcSe 2 ] [PF 6 ]，制备并表征了[dippcSe 2 ] [PF 6 ]，[1-dtbpcSe]
• Synthesis, crystal structure and comparative electrochemistry of metallocenyldiphenylphosphines of ruthenocene, osmocene, ferrocene and cobaltocenium hexafluorophosphate
  作者：Eleanor Fourie、J. Marthinus Janse van Rensburg、Jannie C. Swarts

  DOI：10.1016/j.jorganchem.2013.12.027

  日期：2014.3

  be obtained from a Friedel Crafts reaction between ferrocene and PPh2Cl in the presence of AlCl3 as catalyst. Both the ruthenocene and osmocene derivatives 2 and 3 were obtained by reacting the monolithiated metallocene precursor with PPh2Cl. However, monolithiation of ruthenocene had to be achieved via a stoichiometric amount of tBuLi. For osmocene, monolithiation was achieved by a 20% excess of nBuLi

  茂金属二苯基膦[M（C 5 H 5）（C 5 H 4 PPh 2）]，其中M = Fe（II）（二茂铁= Fc），1，Ru（II）（钌烯基= Rc），2，Os（II） （osmocenyl = OC），3，和Co（III）+ PF 6 -（cobaltocenium六氟磷酸盐= [CC] [PF 6 ]），4，合成和RcPPh的晶体结构2，2，（ž  = 4，单斜，空间组P 2 1 / c）已确定。每种金属茂衍生物的反应性差异使得可以在存在AlCl 3作为催化剂的情况下从二茂铁与PPh 2 Cl之间的Friedel Crafts反应获得1。通过使单片化的茂金属前体与PPh 2 Cl反应，获得了钌茂茂和茂茂茂衍生物2和3。然而，必须通过化学计量的t BuLi来实现钌茂金属的单片化。对于osmocene，通过n BuLi过量20％来实现单片化。未能分离出任何双膦Oc（PPh 2）证明了这一点。
• Structure diversity of silver(I) [1,1′-bis(diphenylphosphino)cobaltocenium] complexes: Effect of counteranions
  作者：Xiang-Hua Wu、Jin-Tao Guan、Shan Jin、Guang-Ao Yu、Xiang-Gao Meng、Sheng-Hua Liu

  DOI：10.1016/j.ica.2009.03.035

  日期：2009.8

  X-ray structural characterizations are recorded for an array of adducts of the form AgX:[dppc][PF 6 ]} n ( n = 1 or 2), [dppc][PF 6 ] = 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate, X = Cl, Br, NO 3 , NO 2 , C 6 H 5 CO 2 , CF 3 CO 2 . Synthetic procedures for all adducts are reported. All compounds have been fully characterised by elemental analysis and spectroscopic techniques. The

  摘要记录了AgX：[dppc] [PF 6]} n（n = 1或2），[dppc] [PF 6] = 1,1'形式的加合物阵列的单晶X射线结构表征。 -双（二苯基膦基）六氟磷酸钴铯，X ＝ Cl，Br，NO 3，NO 2，C 6 H 5 CO 2，CF 3 CO 2。报告了所有加合物的合成程序。所有化合物均已通过元素分析和光谱技术进行了充分表征。对于X ＝ NO 3，NO 2，络合物是单体的[dppc-P，P'] Ag（NO 3）2}或[dppc -P，P′] Ag（NO 2）}，对于X ＝ Cl，Br，C 6 H 5 CO 2，CF 3 CO 2，该络合物为二聚体。
• Synthesis, molecular structure, and molybdenum complexes of 1,1'-bis(diphenylphosphino)cobaltocene
  作者：Daniel L. DuBois、Charles W. Eigenbrot、Alex Miedaner、James C. Smart、R. Curtis Haltiwanger

  DOI：10.1021/om00138a018

  日期：1986.7
• Synthetic and Structural Studies on the Transition-Metal Fullerene Complexes (η²-C₆₀)M[(η⁵-Ph₂PC₅H₄)₂Ru] and (η²-C₆₀)M[(η⁵-Ph₂PC₅H₄)₂Co]⁺(PF₆)^- (M = Pd, Pt) and the Related Compound {[<i>η</i>⁵-Ph₂P(O)C₅H₄]₂Co}⁺(PF₆)^-
  作者：Li-Cheng Song、Guang-Ao Yu、Fu-Hai Su、Qing-Mei Hu

  DOI：10.1021/om049667a

  日期：2004.8.1

  A toluene solution Of C-60 reacted with an equimolar quantity of M(dba)(2) (M = Pd, Pt; dba = dibenzylideneacetone) and (eta(5)-Ph2PC5H4)(2)Ru or with M(PPh3)(4) and (eta(5)-Ph2PC5H4)(2)Ru at room temperature to give the dinuclear transition-metal fullerene complexes (eta(2)-C-60)M [(eta(5)-Ph2PC5H4)(2)Ru] (1, M = Pd; 2, M = Pt), whereas the o-dichlorobenzene solution of C-60 reacted with an equimolar amount of M(dba)(2) and [(eta(5)-Ph2PC5H4)(2)Co](+)(PF6)(-) or with M(PPh3)(4) and [(eta(5)-Ph2PC5H4)(2)Co](+)(PF6)(-) under similar conditions to afford the dinuclear transition-metal fullerene complexes (eta(2)-C-60)M[(eta(5)-Ph2PC5H4)(2)Co](+)(PF6)(-) (3, M = Pd; 4, M = Pt). In addition, the related complex [eta(5)-Ph2P(O)C5H4](2)Co}(+)(PF6)(-) (5) was prepared by oxidation of [(eta(5)-Ph-2-PC5H4)(2)Co](+)(PF6)(-) with an excess amount of aqueous peracetic acid in acetone at room temperature. While 1-4 are the first examples of neutral and cationic dinuclear M/Ru and M/Co (M = Pd, Pt) fullerene complexes, 5 is the first organocobalt Cp complex containing a phosphoryl substituent. All products 1-5 have been fully characterized by elemental analysis, spectroscopy, and X-ray crystal diffraction techniques and, for 1 and 2, by cyclic voltammetry.