Rh(CO)[tBuPCH2(C6H3)CH2PtBu2] | 60399-59-9

• 英文名称: Rh(CO)[tBuPCH2(C6H3)CH2PtBu2]
• 英文别名: (2,6-bis{(di-tert-butylphosphino)methyl}phenyl)carbonylrhodium(III)；(2,6-bis[(di-t-butylphosphino)methyl]phenyl)carbonylrhodium；Rh(CO)[^tBuPCH₂(C₆H₃)CH₂P^tBu₂]；[Rh(2,6-(tBu₂PCH₂)₂C₆H₃)(CO)]；[Rh(PCP-tBu)(CO)]
• CAS: 60399-59-9
• 化学式: C₂₅H₄₃OP₂Rh
• 分子量: 524.469
• InChiKey: DISMKIVOEZBYBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：

  Rh(CO)[tBuPCH2(C6H3)CH2PtBu2] 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  Formation of η² C−H Agostic Rhodium Arene Complexes and Their Relevance to Electrophilic Bond Activation

  摘要：

  Reaction of the ligand 1,3-bis((di-tert-butylphosphino)methyl)benzene (la) with the [RhCO](+) fragment in THF resulted in clean formation of the crystallographically characterized bis-chelated complex 2a which contains an eta(2) agostic Rh C-H bond. Both the NMR data and the X-ray crystal structure show strong interaction between the metal center and the agostic C-H bond, which results in high acidity of the agostic proton. Reaction of 2a with a weak organic base (NEt3 Or collidine) affords the known cyclometalated complex 3. Reaction of the new ligand 1,3-bis((di-tert-butylphosphino)methyl)-4,5,6-trimethoxybenzene (Ib) with the [RhCO](+) fragment in THF gives the analogous to 2a agostic complex 2b. Analysis of the NMR data and the reactivity of both 2a and 2b showed that there is very little, if any, contribution of a metal arenium structure. This interpretation is supported by B3LYP/LANL2DZ density functional calculations on model compounds. Thus, deprotonation of eta(2) aromatic C-H agostic complexes can be proposed as an alternative route,:to electrophilic metalation of aromatic compounds.

  DOI：

  10.1021/ja982534u
• 作为产物：
  描述：

  Rh(H2)[tBuPCH2(C6H3)CH2PtBu2] 在 二氧化碳 作用下， 以 not given 为溶剂， 生成 Rh(CO)[tBuPCH2(C6H3)CH2PtBu2]
  参考文献：
  名称：

  {2,6-双[（二叔丁基膦基）甲基]苯基}二氢铑（III）还原二氧化碳

  摘要：

  DOI：

  10.1021/om00091a003

文献信息

• Carbon Dioxide Reduction by Pincer Rhodium η²-Dihydrogen Complexes:  Hydrogen-Binding Modes and Mechanistic Studies by Density Functional Theory Calculations
  作者：Kuo-Wei Huang、Joseph H. Han、Charles B. Musgrave、Etsuko Fujita

  DOI：10.1021/om060797o

  日期：2007.1.1

  series of pincer PCP−rhodium dihydrogen complexes have been employed to model and examine the proposed mechanisms for the pincer PCP−rhodium complexes mediated hydrogenation of carbon dioxide (CO2). The relative energies of dihydrogen rotamers and dihydride isomers were evaluated together with T1 values to determine the molecular structures of these complexes. We have investigated possible pathways

  使用KMLYP方法对一系列钳式PCP-铑二氢络合物进行密度泛函理论（DFT）计算，已为拟议的钳式PCP-铑络合物介导的二氧化碳（CO 2）加氢机理建模并进行了研究。与T 1值一起评估了二氢旋转异构体和二氢异构体的相对能量，以确定这些配合物的分子结构。我们已经研究了涉及二氢化铑物种形成的CO 2还原过程的可能途径。尽管二氢配合物比相应的二氢化物异构体更稳定，但CO 2的还原必须通过二氢化物结构进行。
• Transition metal–carbon bonds. Part XLII. Complexes of nickel, palladium, platinum, rhodium and iridium with the tridentate ligand 2,6-bis[(di-t-butylphosphino)methyl]phenyl
  作者：Christopher J. Moulton、Bernard L. Shaw

  DOI：10.1039/dt9760001020

  日期：——

  The bulky diphosphine 1,3-[(di-t-butylphosphino)methyl]benzene undergoes metallation very readily to give a new type of tridentate chelating system, 2,6-bis[(di-t-butylphosphino)methyl]phenyl (pcp). Complexes prepared are of the types [MX(pcp)](M = Ni, Pd, or Pt; X = Cl, Br, H, C⋮CPh, or CN; M = Rh, X = CO), [MHCl(pcp)](M = Rh or Ir), and [IrHCl(CO)(pcp)]. [Ni(CO)(pcp)][BPh4] was also prepared. 1H-

  庞大的二膦1,3-[（二叔丁基膦基）甲基]苯很容易进行金属化反应，从而得到一种新型的三齿螯合体系，即2,6-双[（二叔丁基膦基）甲基]苯基（pCP ）。制备的复合物的类型为[MX（pCP）]（M = Ni，Pd或Pt； X = Cl，Br，H，C⋮CPh或CN； M = Rh，X = CO），[MHCl（pCP ）]（M = Rh或Ir）和[IrHCl（CO）（pCP）]。还制备了[Ni（CO）（pCP）] [BPh 4 ]。给出了1 H-和31 P-nmr数据以及ir数据。
• Kinetics and Thermodynamics of Small Molecule Binding to Pincer-PCP Rhodium(I) Complexes
  作者：Mark D. Doherty、David C. Grills、Kuo-Wei Huang、James T. Muckerman、Dmitry E. Polyansky、Rudi van Eldik、Etsuko Fujita

  DOI：10.1021/ic300672g

  日期：2013.4.15

  The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH2PtBu2] (1) and Rh[tBu2P(CH2)2(CH)(CH2)2PtBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium

  几个小分子L（L = N 2，H 2，D 2和C 2 H 4）与配位不饱和钳式PCP铑（I）配合物Rh [ t Bu 2 PCH 2（C 6 H 3）CH 2 P t Bu 2 ]（1）和Rh [ t Bu 2 P（CH 2）2（CH）（CH 2）2 P t Bu 2 ]（2结合动力学快速光解法，NMR平衡研究和密度泛函理论（DFT）计算，研究了有机溶剂（正庚烷，甲苯，THF和环己烷d 12）中的）。使用各种气体混合物并通过NMR监测直至建立平衡，发现环己烷-d 12中N 2，H 2和C 2 H 4的结合相对自由能按C 2 H 4
• Formation of Difluoromethylene−Arenium Complexes by Consecutive Aryl−CF₃ C−C Bond Activation and C−F Bond Cleavage
  作者：Milko E. van der Boom、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/ja990779g

  日期：1999.7.1

  Oxidative addition of one of the strongest C-C bonds, Aryl-CF3, to Rh(I) takes place upon Creating 1-CF3-2,6-((CH2PBu2)-Bu-t)(2)-C6H3 (1, PCP) with [RhClL2](2) (L = C2H4 or C8H14) in dioxane or toluene at elevated temperatures leading to quantitative formation of Rh(CF3)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl (2-Cl). The iodide analogue 2-I was prepared by reacting Rh(eta(1)-N-2)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3) (3) with CF3I at room temperature. ArCF2-F bond cleavage was not observed in parallel to the C-C bond activation. Treating a dioxane solution of the thermally stable Rh-III-CF3 complexes 2-Cl,I with excess trifluoromethanesulfonic acid (HOTf) at room temperature resulted in C-F bond cleavage and selective formation of the unique difluoromethylene-arenium complexes [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)X][OTf] (4; X = Cl, I) which were characterized spectroscopically by NMR, UV/vis, and ED-MS. No reaction was observed with HCl. Reaction of 2-Cl with BF3 or Ph3CBF4 (trityl cation) also resulted in C-F bond cleavage to give [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl]BF4 (10).
• Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity
  作者：Milko E. van der Boom、Shyh-Yeon Liou、Yehoshoa Ben-David、Linda J. W. Shimon、David Milstein

  DOI：10.1021/ja9738889

  日期：1998.7.1

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).