(1,1,1-tris(dimethylphosphinomethyl)ethane)trichlororhodium(III) | 183323-69-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (1,1,1-tris(dimethylphosphinomethyl)ethane)trichlororhodium(III)
• 英文别名: trichloro[1,1,1-tris(dimethylphosphinomethyl)ethane]rhodium(III)；[1,1,1,-tris((dimethylphosphino)methyl)ethane]RhCl3；[RhCl3(1,1,1-tris(dimethylphosphinomethyl)ethane)]；[RhCl3(tdmme)]；[3-dimethylphosphanyl-2-(dimethylphosphanylmethyl)-2-methylpropyl]-dimethylphosphane;trichlororhodium
• CAS: 183323-69-5
• 化学式: C₁₁H₂₇Cl₃P₃Rh
• 分子量: 461.521
• InChiKey: VTJRNODTDRVUKA-UHFFFAOYSA-K

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：
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• 环数：
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• 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：

  (1,1,1-tris(dimethylphosphinomethyl)ethane)trichlororhodium(III) 以 水 、 重水 为溶剂， 生成 [Rh(1,1,1-tris(dimethylphosphinomethyl)ethane)(H2O)3](3+)
  参考文献：
  名称：

  含1,1,1-三（二甲基膦基甲基）乙烷（tdmme）的铑（III）配合物的制备和表征。[RhX 3（tdmme）]（X = Cl，Br或I），[Rh（NH 3）3（tdmme）] 3+和[{Rh（tdmme）} 2（µ-X）3 ] 3+的结构（X = Cl或OH）在固态和溶液中

  摘要：

  合成了几种新的含三脚架三齿膦MeC（CH 2 PMe 2）3（tdmme）的铑（III）配合物，并在固态和溶液中对其结构进行了研究。单晶X射线分析显示，与苯基取代的类似物MeC（CH 2 PPh 2）3（tdpme）相比，tdmme具有更小的空间需求和更强的反式影响。单核三氯配合物[RhCl 3（tdmme）] 1中的长Rh-Cl键由于tdmme的强反式影响，使得该配合物在水中具有反应性。1的结构表征了溶液中的氯仿及其与某些酸或碱的反应产物。三重氯桥联双核络合物[{Rh（tdmme）} 2（µ-Cl）3 ] [BF 4 ] 3，在水中也显示出结构变化，而单核三胺络合物[Rh（NH 3）3（ tdmme）] [BF 4 ] 3和三羟基桥连双核络合物[{Rh（tdmme）} 2（µ-OH）3 ] [BF 4 ] 3稳定。tdmme配合物的吸收光谱表明，tdmme对铑的配体场更强（III）的中心

  DOI：

  10.1039/dt9960003779
• 作为产物：
  描述：

  氯化铑(三水) 、 1,1,1-tris(dimethylphosphinomethyl)ethane 以 乙醇 为溶剂， 生成 (1,1,1-tris(dimethylphosphinomethyl)ethane)trichlororhodium(III)
  参考文献：
  名称：

  XPS Investigations of (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe₃ and [1,1,1-tris((dimethylphosphino)methyl)ethane]RhMe₃ and Their Rh−C Cleavage Derivatives. Comparison of Hard- and Soft-Ligated Rhodium Organometallics

  摘要：

  The new molecules P(3)RhMe(3-n)(OTf)(n) are reported (n = 0-2; P-3 = MeC(CH(2)PMe(2))(3); OTf = OS(O)(2)CF3). The known fac-(Me(3)P)(3)RhMe(3) was converted to mer-(Me(3)P)(3)RhMe(3-n)Cl(n). (n = 1, 2) by cleavage with HCl in ether. X-ray photoelectron spectra (XPS) of these were recorded, and all except the P(3)RhMe(3-n)Cl(n) series afforded clean spectra. XPS were also obtained for the known CnRhMe(3-n)X(n) (n = 0-2; X = Cl, Br, OTf; Cn = 1,4,7-trimethyl-1,4,7-triazacyclononane), CnRhX(3) (X = Cl, Br), CnRhMe(OH)(OTf), and [CnRhMe(2)(CO)]OTf. An X-ray crystal structure of P(3)RhMe(3) is reported, and the geometry at the metal is compared among P(3)RhMe(3), (Me(3)P)(3)RhMe(3), and CnRhMe(3). Core binding energies (BEs) for the series L(3)RhMe(3-n)X(n) (L(3) = Cn, P-3) change linearly with n for a given L(3) and X. For CnRhMe(3-n)X(n), replacement of methyl by chloride or bromide gives similar Delta BE values (similar to 0.7 eV), while triflate-for-methyl substitution gives a much larger Delta BE (1.2 eV). Triflate-for-methyl substitution in P(3)RhMe(3-n)(OTf)(n), however, causes a Delta BE of only 0.8 eV. Thus, the Rh(3d(5/2)) core binding energies in these complexes change less in triflate-for-methyl substitutions when the P-3 ancillary ligand is present than in the presence of Cn; apparently P-3 compensates for changes in electron density at the rhodium center more effectively than does Cn, presumably as a result of the greater polarizability of phosphorus (softer) compared to nitrogen (harder). The XPS trends for these series effectively mean that P-3 makes Rh-III a softer metal and Cn makes Rh-III a harder metal.

  DOI：

  10.1021/om9601099

文献信息

• Preparation, crystal structures and spectroscopic properties of novel [MIIICl3−(P)3+]+ (M = Co, Rh; n= 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane
  作者：Takayoshi Suzuki、Toshiaki Tsukuda、Masakazu Kiki、Sumio Kaizaki、Kiyoshi Isobe、Hideo D. Takagi、Kazuo Kashiwabara

  DOI：10.1016/j.ica.2005.02.008

  日期：2005.5

  Cobalt(III) and rhodium(III) complexes of the series of [MIIICl3 − n(P)3 + n]n+ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M–P and M–Cl bond lengths were dependent primarily on the strong trans influence of the

  制备了[M III Cl 3-  n（P）3 +  n ] n +（M = Co或Rh; n  = 0、1、2或3）系列的钴（III）和铑（III）配合物使用1,1,1-三（二甲基膦基甲基）乙烷（tdmme）和单或二齿膦。两个系列配合物的单晶X射线分析表明，M–P和M–Cl键的长度主要取决于磷化氢的强反式影响，其次取决于金属中心周围的空间拥挤。几个膦基的配合。实际上，M–P（tdmme）键的长度按[MCl 3（tdmme）] <[MClCo III和Co III的2（tdmme）（PMe 3）] +  <[MCl（tdmme）（dmpe）] 2+（dmpe = 1,2-双（二甲基膦基）乙烷）<[M（tdmme）2 ] 3+ Rh III系列配合物，而M–Cl键长度以此顺序缩短（[M（tdmme）2 ] 3+除外）。金属中心周围的这种空间拥堵还可以解释一系列配合物[MCl（tdmme）（dmPM，dmpe或dmpp）]
• Preparation, crystal structures and spectroscopic properties of chloro(pentane-2,4-dionato){1,1,1-tris(dimethylphosphinomethyl)ethane}chromium(III), cobalt(III) and rhodium(III) hexafluorophosphate: comparison of the MP, MCl and MO (M=Cr, Co and Rh) bond lengths among the three MIII complexes
  作者：Takayoshi Suzuki、Takeshi Imamura、Sumio Kaizaki、Kazuo Kashiwabara

  DOI：10.1016/s0277-5387(02)00859-8

  日期：2002.4

  Three metal(III)-tripodal tridentate phosphine complexes of the formula [MCl(acac)(tdmme)]PF6, where M = Cr, Co or Rh; acac = pentane-2,4-dionate; tdmme = 1,1,1-tris(dimethylphosphinomethyl)ethane, were prepared and their molecular and crystal structures and spectroscopic properties examined. All the complexes crystallized in an isomorphous space group P2(1)2(1)2(1), which is indicative of spontaneous resolution of the enantiomeric pair. The Cr-P bond lengths in [CrCl(acac)(tdmme)]PF6 (average 2.437 Angstrom) are remarkably longer than the corresponding Co-P (average 2.201 Angstrom) and Rh-P (average 2.252 Angstrom) ones. The longer and therefore the weaker Cr-P bonds may explain the relatively weak trans influence of the -PMe2 group in [CrCl(acac)(tdmme)]PF6; among the three Mill complexes, the elongation of M-O bond lengths in [MCl(acac)(tdmme)]PF6 from those in [M(acac)(3)] has been found to be Cr(III) (0.016 Angstrom) < Co-III (0.059 angstrom) < Rh-III (0.096 Angstrom), indicating a much weaker trans influence of the -PMe2 group in the Cr-III complex than in the Co-III and Rh-III, complexes. The first d-d transition band of [CrCl(acac)(tdmme)](+) was observed at 18590 cm(-1). This is appreciably smaller than the corresponding band of the Coin complex at 20960 cm(-1), suggesting the ligand-field strength of tdmme is fairly weak in the Cr-III complex. The ligand-field strength Delta and the Racah's B parameters of [CrCl(acac)(tdmme)](+) were also discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.