RuCl2(o-(diphenylphosphino)-N,N-dimethylaniline)(PPh3) | 196940-60-0

• 英文名称: RuCl2(o-(diphenylphosphino)-N,N-dimethylaniline)(PPh3)
• 英文别名: RuCl2([o-(N,N-dimethylamino)phenyl]diphenylphosphine)(PPh3)；trans-RuCl2-(o-diphenylphosphino-N,N’-dimethylaniline)(PPh3)；trans-RuCl2(o-diphenylphosphino-N,N’-dimethylaniline)(PPh3)；trans-RuCl2(o-diphenylphosphino-N,N'-dimethylaniline)；trans-[RuCl2(o-diphenylphosphino-N,N-dimethylaniline)(PPh3)]
• CAS: 196940-60-0
• 化学式: C₃₈H₃₅Cl₂NP₂Ru
• 分子量: 739.626
• InChiKey: BFCJDUHWFJLQEW-UHFFFAOYSA-L

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：

  RuCl2(o-(diphenylphosphino)-N,N-dimethylaniline)(PPh3) 在 air 作用下， 以 not given 为溶剂， 生成 [Ru(III)Cl([o-(N,N-dimethylamino)phenyl]diphenylphosphine)]2(μ-o)(μ-Cl)2
  参考文献：
  名称：

  Ruthenium(II) Thiol and H₂S Complexes: Synthesis, Characterization, and Thermodynamic Properties

  摘要：

  The known, green, five-coordinate species trans-RuCl2(P-N)(PPh3) react with R'SH thiols to give yellow cis-RuCl2(P-N)(PPh3)(R'SH) products (P-N = o-diphenylphosphino-N,N'-dimethylaniline; R' = alkyl). The MeSH and EtSH compounds are structurally characterized, with the former being the first reported for a transition metal MeSH complex, while the thiol complexes with R' = Pr-n, Pr-i, (n)Pn (pentyl), (n)Hx (hexyl), and Bn (benzyl) are synthesized in situ. Other trans-RuX2(P-N) (PR3) complexes (X = Br, I; R = Ph, p-tolyl) are synthesized, and their H2S adducts, of a type reported earlier by our group, are also prepared. Thermodynamic data are presented for the reversible formation of the MeSH and EtSH complexes and the H2S analogues. The (RuCl2)-Cl-II(P-N)(PPh3) complex in solution decomposes under O-2 to form [(RuCl)-Cl-III(P-N)](2)(mu-O)(mu-Cl)(2).

  DOI：

  10.1021/ic3004118
• 作为产物：
  描述：

  生成 RuCl2(o-(diphenylphosphino)-N,N-dimethylaniline)(PPh3)
  参考文献：
  名称：

  水，甲醇和乙醇与五配位钌（ii）配合物的可逆结合†

  摘要：

  已知的绿色五坐标方形金字塔式反RuCl 2（PN ）（PPh 3）络合物可逆结合水， 甲醇 和 乙醇在固态和CH 2 Cl 2溶液中的空位配位点上生成粉红色加合物（PN =邻二苯基膦基氮，N'-二甲基苯胺）。加合物具有良好的特征，包括对水合络合物反式-RuCl 2（PN ）（PPh 3）（H 2 O）的X射线分析，其以两种不同的苯溶剂化形式结晶。结构数据与先前确定的H 2 S，硫醇和H 2结合的结构数据的比较，它们形成顺式-RuX 2（P–N）（PPh 3）L产物（X = Cl，Br; L = a S-配体或H 2）显示反式影响趋势P> H 2 S〜硫醇> H 2 > Cl〜Br >高氧2。用于绑定的热力学数据水通过UV-Vis光谱，并在Δ溶液估计ħ ø在固体状态下的Aqua和醇的加合物的数据通过差示扫描量热法获得。包括已公开的S-配体加合物数据，揭示了当MeSH>时，固体配合物的热稳定性趋势。甲醇>

  DOI：

  10.1039/c3dt32909g

文献信息

• Comparative properties of coordinated H2 and H2S at a ruthenium(ii) centre
  作者：Erin S. F. Ma、Dona C. Mudalige、Brian O. Patrick、Brian R. James

  DOI：10.1039/c3dt50314c

  日期：——

  Thermodynamic data for the reversible formation of cis-RuCl2(P–N)(PPh3)(η2-H2) (2a) from trans-RuCl2(P–N)(PPh3) in C6D6 are determined by variable temperature 31P1H} and 1H NMR spectroscopy; P–N = o-diphenylphosphino-N,N′-dimethylaniline. Values of ΔH° = −26 ± 4 kJ mol−1, ΔS° = −40 ± 15 J mol−1 K−1, and ΔG° (at 25 °C) = −13.8 ± 0.2 kJ mol−1 are compared with recently reported data for the corresponding H2S adduct (4a), where the exothermicity is greater by ∼20 kJ mol−1, but this is counteracted by a more unfavourable entropy change, and overall the K and ΔG° values at 25 °C are close. For loss of H2 from 2a in the solid state, whose X-ray structure is presented, ΔH° is 50 ± 3 kJ mol−1 as measured by Differential Scanning Calorimetry. The pKa values of the coordinated H2 (∼11) and H2S (∼14) are estimated by reactions of 2a and 4a with proton sponge (1,8-bis(dimethylamino)naphthalene) in CD2Cl2 at 20 °C; the mono-hydrido and -mercapto products are identified in situ. A corresponding H2O adduct is not deprotonated under the same conditions. Related dihydrido, mercapto and hydroxy species are formed by in situ reactions of 1a with NaH, NaSH, and NaOH, respectively.

  C6D6 中反式 RuCl2(P–N)(PPh3) 可逆形成顺式 RuCl2(P–N)(PPh3)(η2-H2) (2a) 的热力学数据由可变温度 31P1H} 和1H核磁共振波谱； P–N = 邻二苯基膦-N,N'-二甲基苯胺。 ΔH° = −26 ± 4 kJ mol−1、ΔS° = −40 ± 15 J mol−1 K−1 和 ΔG°（25 °C 时）= −13.8 ± 0.2 kJ mol−1 的值与最近报道了相应的 H2S 加合物 (4a) 的数据，其中放热性增大了 ∼20 kJ mol−1，但这被更不利的熵变化所抵消，总体而言，25 °C 时的 K 和 ΔG° 值很接近。对于固态 2a 中 H2 的损失，其 X 射线结构如图所示，通过差示扫描量热法测量，ΔH° 为 50 ± 3 kJ mol−1。配位的 H2 (∼11) 和 (∼14) 的 pKa 值通过 2a 和 4a 与质子海绵（1,8-双（二​​甲氨基）萘）在 CD2Cl2 中在 20 °C 下的反应来估算；原位鉴定一氢和-巯基产物。相应的 H2O 加合物在相同条件下不会去质子化。相关的二氢基、巯基和羟基物种分别通过 1a 与 NaH、NaSH 和 NaOH 的原位反应形成。
• Binding of CO and NH3 at a five-coordinate Ru(ii) centre in the solid state and in solution
  作者：Erin S. F. Ma、Dona C. Mudalige、Brian R. James

  DOI：10.1039/c3dt51625c

  日期：——

  however, generate a species, speculatively thought to be the unusual, tight ion-pair, bisammine species [RuX(P–N)(PPh3)(NH3)2⋯X], 5a (X = Cl) and 5b (X = Br), in which a halide is considered strongly H-bonded to the cis-ammine ligands, although an alternative RuX(P–N)(PPh3)(NH3)2 formulation with a monodentate P–N ligand cannot be ruled out; dissolution in CDCl3 of isolated 5a and 5b, which are characterized

  已知的五配位，四方锥，绿色反-RuCl 2（P-N）（PR 3）配合物（P-N = Ö -diphenylphosphino- Ñ，Ñ '二甲基苯胺; R =苯基（1A），p -在室温下处于固态或在低温下于CDCl 3溶液中配位的CO（在1个大气压下）形成米色反式-单羰基衍生物。在室温下的溶液反应中，PR 3配体解离，形成黄色的二羰基络合物RuCl 2（CO）2（PN ），形成反式，顺-和顺，顺式异构体。通过使用13 CO，羰基配合物的特征在于可变温度NMR和IR数据，以及（对于单羰基而言）元素分析。同样，固态的1a和二溴类似物（1b）结合NH 3以形成米色反-monoammine物种RUX 2（P-N）（PPH 3）（NH 3），反式-图4a（X = C1）和反式-图4b（X =溴），与顺式P-原子。然而，溶液NH 3反应产生了一种物质，推测是一种不寻常的，紧密的离子对的双胺类物质[RuX（P–N）（PPh
• Reactions of phenylacetylene and p-tolylacetylene with a five-coordinate RuII complex
  作者：Erin S.F. Ma、Brian O. Patrick、Brian R. James

  DOI：10.1016/j.ica.2013.09.009

  日期：2013.11

  The acetylenes R'C CH react with the known 5-coordinate, green, square-pyramidal trans-RuCl2(P-N)(PR3) complexes (R', R = Ph, p-tolyl; P-N = o-diphenylphosphino-N, N'-dimethylaniline) in CH2Cl2 solution to form the orange vinylidene derivatives, cis-RuCl2(P-N)(PR3)(C@ C(H) R')(2); this is a well-known type reaction, but is the first to involve a bidentate P-N ligand, and convert a 5-coordinate precursor to a 6-coordinate product. Crystal structure and P-31H-1} NMR data for the R = R' = Ph complex (2a), extend significantly an established linear correlation between the Ru-P bond length (within the P-N ligand) and the P-31H-1} chemical shift of this P-atom. Complex 2a reacts with H2S to form the thioaldehyde species cis-RuCl2(P-N)(PPh3)(SCHCH2Ph), and reacts with H2O to form poorly characterized carbonyl species; the reactivity resembles that of an earlier studied Ru-PNP species, where PNP = Me(CH2) 2N[(CH2)(2)PPh2] 2. (C) 2013 Elsevier B. V. All rights reserved.
• The Nitrous Oxide Complex, RuCl₂(η¹-N₂O)(P−N)(PPh₃) (P−N = [<i>o</i>-(<i>N,N</i>-Dimethylamino)phenyl]diphenylphosphine); Low Temperature Conversion of N₂O to N₂ and O₂
  作者：Craig B. Pamplin、Erin S. F. Ma、Nasser Safari、Steven J. Rettig、Brian R. James

  DOI：10.1021/ja0106319

  日期：2001.9.1
• Synthesis and X-ray Structure of an H₂S Complex, RuCl₂(P-N)(P(<i>p</i>-tolyl)₃)(SH₂) (P-N = <i>o</i>-(Diphenylphosphino)-<i>N</i>,<i>N</i>-dimethylaniline)
  作者：D. Chandrika、Erin S. Ma、Steven J. Rettig、Brian R. James、William R. Cullen

  DOI：10.1021/ic9707772

  日期：1997.11.1