Rh(η⁵-C₅Me₅)Cl₂(1,3,5-triaza-7-phosphaadamantane) | 908356-25-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: Rh(η⁵-C₅Me₅)Cl₂(1,3,5-triaza-7-phosphaadamantane)
• 英文别名: Rh(η5-C5Me5)(pta)Cl2；(η5-C5Me5)RhCl2(1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane)；[(pentamethylcyclopentadienyl)RhCl2(1,3,5-triaza-7-phosphaadamantane)]；(η5-pentamethylcyclopentadienide)dichloro(1,3,5-triaza-7-phosphaadamantane)rhodium(III)；[Rh(η5-C5Me5)(1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane)Cl2]；[Cp*RhCl2(7-phospha-1,3,5-triazaadamantane)]；1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane;dichloride
• CAS: 908356-25-2
• 化学式: C₁₆H₂₇Cl₂N₃PRh
• 分子量: 466.196
• InChiKey: JLOFDGMEILCMBR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -2.89
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Rh(η⁵-C₅Me₅)Cl₂(1,3,5-triaza-7-phosphaadamantane) 、 sodium tetrahydroborate 以 乙醇 为溶剂， 以79.3%的产率得到[(pentamethylcyclopentadienyl)RhH2(1-boranyl-1,3,5-triaza-7-phosphaadamantane)]
  参考文献：
  名称：

  使用 Ru(II) 和 Rh(III) RAPTA 型催化剂在温和条件下酸辅助 CO2 加氢生成甲醇

  摘要：

  使用单分子定义的钌和铑 RAPTA 型催化剂 [Ru(η 6 - p -cymene)X 2 (PTA)] (X = I( 1 )) 从 CO 2生产 CH 3 OH 的高效均相催化剂体系， Cl( 2 ); PTA = 1,3,5-三氮杂-7-磷金刚烷) 和铑催化剂 [Rh(η 5 -C 5 Me 5 )X 2 (PTA/PTA-BH 3 )] (X = Cl( 3 ), H( 4 ) 和 PTA-BH 3 , H( 5 )) 在温和条件下在酸性介质中发育。使用[Ru(η 6 - p -伞花烃)I 2 (PTA)]催化剂实现4752的TON，这代表了使用单分子定义的Ru和Rh RAPTA型催化剂将CO 2加氢为CH 3 OH的第一个实例。

  DOI：

  10.1039/d1cc03049c
• 作为产物：
  描述：

  [(pentamethylcyclopentadienyl)RhCl2(1-boranyl-1,3,5-triaza-7-phosphaadamantane)] 在 water 作用下， 以 丙酮 为溶剂， 生成 Rh(η⁵-C₅Me₅)Cl₂(1,3,5-triaza-7-phosphaadamantane)
  参考文献：
  名称：

  Synthesis and reactivity of rhodium(III) pentamethylcyclopentadienyl complexes of N–B–PTA(BH3): X-ray crystal structures of [Cp∗RhCl2{N–B}–PTA(BH3)] and [Cp∗Rh{N–B–PTA(BH3)}(η2-CH2=CHPh)]

  摘要：

  The reaction between 1-boranyl-1,3,5-triaza-7-phosphaadamantane ligand N-B-PTA(BH(3)) and [Cp*RhCl(mu-Cl)](2) affords [Cp*Rh{N-B-PTA(BH(3))}Cl(2)] (3) or [Cp*Rh{N-B-PTA(BH(3))}(2)Cl]Cl (5) containing one or two P-bonded boronated PTA ligands. The hydride [Cp*Rh{N-B-PTA(BH(3))}H(2)] (8) was also obtained by reaction of 3 with NaBH(4) and alternatively by direct hydroboration of [Cp*Rh(PTA)Cl(2)] with excess NaBH(4). Moderately slow hydrolysis of the N-boranyl rhodium complexes affords dihydrogen, H(3)BO(3) and the corresponding PTA derivatives, including the water-soluble dihydride [Cp*Rh(PTA)H(2)] (9). Finally, the reaction of 8 with electron poor alkynes gives the alkene complexes [Cp*Rh{N-B-PTA(BH(3))}(eta(2)-CH(2) = CHR)] (R = Ph, 10; C(O)OEt, 11) as a mixture of rotamers eta(2)-coordinated to rhodium without affecting the N-BH(3) moiety. The X-ray crystal structures of 3 and 10 were also obtained and are here discussed. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.04.006

文献信息

• Counterion-dependent deuteration of pentamethylcyclopentadiene in water-soluble cationic Rh(iii) complexes assisted by PTA
  作者：Gianluca Ciancaleoni、Sandra Bolaño、Jorge Bravo、Maurizio Peruzzini、Luca Gonsalvi、Alceo Macchioni

  DOI：10.1039/c003056m

  日期：——

  [Cp*RhCl(PTA)2]X (PTA = 7-phospha-1,3,5-triazaadamantane) undergoes an H/D exchange process between the methyl groups of Cp* and D2O whose rate depends on the coordinating ability of the counterion X−. Kinetic studies and DFT calculations indicate that deuteration involves the abstraction of a Me-Cp* proton by a coordinated OH−; the formation of the latter seems to be facilitated by the presence of the N-basic centers of PTA.

  [Cp*RhCl(PTA)2]X（PTA = 7-磷-1,3,5-三氮杂金刚烷）在 Cp* 的甲基和 D2O 之间经历了一个 H/D 交换过程，其速率取决于反离子 X- 的配位能力。动力学研究和 DFT 计算表明，氘化涉及配位 OH- 对 Me-Cp* 质子的抽取；PTA 的 N 碱中心的存在似乎促进了后者的形成。
• In Vitro Evaluation of Rhodium and Osmium RAPTA Analogues:  The Case for Organometallic Anticancer Drugs Not Based on Ruthenium
  作者：Antoine Dorcier、Wee Han Ang、Sandra Bolaño、Luca Gonsalvi、Lucienne Juillerat-Jeannerat、Gàbor Laurenczy、Maurizio Peruzzini、Andrew D. Phillips、Fabrizio Zanobini、Paul J. Dyson

  DOI：10.1021/om060394o

  日期：2006.8.1

  Reaction of the dimer [(eta(5)-C5Me5)RhCl(mu(2)-Cl)](2) with 2 or 4 equiv of the water-soluble phosphine 1,3,5-triaza-7-phosphatricyclo[3.3.1.1] decane (pta) affords [Rh(eta(5)-C5Me5)(pta)Cl-2] and [Rh(eta(5)-C5Me5)(pta)(2)Cl] Cl, respectively. Both complexes have been characterized in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction, the latter as the chloride and BPh4- salts. In addition, the rhodium(I) complexes [Rh(eta(5)-C5Me5)(CO)(pta)] and [Rh(eta(5)-C5H5)(pta)(2)] have been prepared lfrom [Rh(eta(5)-C5Me5)(CO)(2)] and [Rh(eta(5)-C5H5)(PPh3)(2)], respectively, by reaction with pta. An in vitro evaluation of these compounds, together with [Os(eta(6)-C10H14)(pta)Cl-2] and the well-characterized antimetastasis drug [Ru(eta(6)-C10H14)(pta)Cl-2], RAPTA-C, was undertaken using HT29 colon carcinoma, A549 lung carcinoma, and T47D breast carcinoma cells. In the HT29 cell line, the two nearest congeners to [Ru(eta(6)-C10H14)(pta)Cl-2], viz., [Rh(eta(5)-C5Me5)(pta)Cl-2] and [Os(eta(6)-C10H14)(pta)Cl-2], demonstrated very similar cytotoxicity profiles. [Rh(eta(5)-C5Me5)(pta)Cl-2] proved significantly more cytotoxic in A549 cells and [Rh(eta(5)-C5Me5)(pta)(2)Cl] Cl 3-fold more cytotoxic in T47D cells, both relative to RAPTA-C. These data suggest that the development of organometallic anticancer drugs based on the neighboring elements to ruthenium should not be overlooked.
• New highly water-soluble rhodium complexes bearing 1,3,5-triaza-7-phosphaadamantane (PTA) and/or tris(hydroxymethyl) phosphine (THP)
  作者：Sandra Bolaño、Maider Plaza、Jorge Bravo、Jesús Castro、Maurizio Peruzzini、Luca Gonsalvi、Gianluca Ciancaleoni、Alceo Macchioni

  DOI：10.1016/j.ica.2009.05.041

  日期：2010.2

  A family of cationic and neutral highly water-soluble rhodium complexes [Cp*Rh(PTA)(3)]Cl-2 (1), [Cp*RhCl2(THP)] (2), [Cp*RhCl(THP)(2)]Cl (3), and [Cp*RhCl(PTA)(THP)] Cl (4) have been synthesised and fully characterised [PTA = 1,3,5-triaza-7-phosphaadamantane; THP = tris(hydroxymethyl) phosphine]. Their water-solubility increases as the number of the phosphines coordinated to the metal centre is increased. The X-ray crystal structure of compound 2 was obtained and shows the presence of intermolecular hydrogen bonding. NMR speciation studies of [Cp*RhCl2(PTA)] in deuterated water show the existence of several equilibria involving substitution processes in which the water molecules can substitute both chloride and PTA ligands. (C) 2009 Elsevier B. V. All rights reserved.