tetraphenylarsonium dicarbonyldiiodorhodate(I) | 95246-85-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tetraphenylarsonium dicarbonyldiiodorhodate(I)
• 英文别名: carbon monoxide;diiodorhodium(1-);tetraphenylarsanium
• CAS: 95246-85-8；13986-81-7
• 化学式: C₂I₂O₂Rh*C₂₄H₂₀As
• 分子量: 796.08
• InChiKey: QATPPHIKZKMTDY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tetraphenylarsonium dicarbonyldiiodorhodate(I) 在 氢碘酸 作用下， 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  The Characterization of HRh(CO)2I3- and EtCORh(CO)2I3-: Two Key Intermediates in Rhodium-Catalyzed Carbonylation of Ethylene

  摘要：

  DOI：

  10.1021/ja00082a061
• 作为产物：
  描述：

  (Ph4As)[Rh(CO)(COC2H5)I3] 以 二苯醚 、 氯仿 为溶剂， 生成 tetraphenylarsonium dicarbonyldiiodorhodate(I)
  参考文献：
  名称：

  烷基卤化物向铑（I）和铱（I）二羰基二碘化物的氧化加成：醇催化羰基化的关键反应

  摘要：

  Alkyl iodides (RI) react with [Rh(CO)2I2]- to give acyl species [Rh(CO)(COR)I3]- (R = Et, (n)Pr, (i)Pr) and with [Ir(CO)2]2]- to give alkyl complexes [RIr(CO)2]2]- (R = Et, (n)Pr, (i)Pr, (n)Bu, n-C5H11, n-C6H13). The reactions are analogous to the known reactions of MeI with [Rh(CO)2I2]- and [Ir(CO)2I2]-. The products are characterized spectroscopically and by an X-ray crystal structure determination for Ph4As[(n-C6H13)Ir(CO)2I3] which showed a fac,cis geometry for the anion. [Crystal structure data: monoclinic, a = 9.408(7) angstrom, b = 19.470(16) angstrom, c = 19.529(12) angstrom, beta = 94.99(5)-degrees, Z = 4, space group P2(1)/n (a nonstandard setting of P2(1)/c C2h5, No. 14); 2446 independent reflections (of 5197 measured) for which \F\/sigma(\F\) > 4.0; R = 0.0966 (R(w) = 0.0921, 238 parameters)]. Kinetic data for the reactions of [Rh(CO)2I2]-with EtI. (n)PrI, and (i)PrI and for [Ir(CO)2I2]- with MeI, EtI, and (n)PrI show that oxidative addition of Ri to [M(CO)2I2]- is first-order in both reactants. For M = Rh, reactions showed clean second-order kinetics below 80-degrees-C, though some decomposition occurred at higher temperatures. For M = Ir, clean second-order kinetics were observed with MeI, but reactions with EtI and (n)PrI showed a more complex kinetic behavior. A competing radical pathway is suggested, which can be quenched by added duroquinone. Second-order rate constants, k2, evaluated over the temperature ranges 70-80-degrees-C (M = Rh) and 35-50-degrees-C (M = Ir) gave the following activation parameters: (M = Rh) DELTAH(double dagger)/kJ mol-1 = 50(+/-1) (R = Me), 56(+/-10) (R = Et), 51(+/-10) (R = (n)Pr), 61(+/-15) (R = (i)Pr); DELTAS(double dagger)/J mol-1 K-1 = -165(+/-4) (R = Me), -195(+/-25) (R = Et), -215(+/-25) (R = (n)Pr), -180(+/-30) (R = (i)Pr); (M = Ir) DELTAH(double dagger)/kJ mol-1 = 54(+/-1) (R = Me), 66(+/-5) (R = Et), 66(+/-3) (R = (n)Pr); DELTAS(double dagger)/J mol-1 K-1 -113(+/-4) (R = Me), -123(+/-15) (R = Et), -132(+/-11) (R = (n)Pr). Comparisons are made between the reactions of methyl iodide and the higher alkyl iodides with both [Rh(CO)2I2]-(relative rates: Me, 1000, Et, 3; (n)Pr, 1.7) and [Ir(CO)2I2]- (relative rates: Me, 1000; Et, 2.3; (n)Pr, 0.75). The similarity to reactivity trends for organic nucleophiles suggests an SN2 mechanism, but with a competing radical pathway for iridium. Relative rates for the two nucleophiles, k(Ir)/k(Rh) ca. 150 (R = Me), 220 (R = Et), and 140 (R = (n)Pr), are estimated. Alkyl isomerization (iso --> n) is observed for both [Rh(CO)(COPr)I3]- and (PrIr(CO)2I3]- and displacement of propene from [Rh(CO)(COPr)I3]- by added ethene gives [Rh(CO)(COEt)Is]-reversibly. A mechanism involving hydridoalkene intermediates is proposed. The data are consistent with the carbonylation of the higher alcohols (ROH) proceeding via rate determining oxidative addition of RI to [Rh(CO)2I2]-, rather than by a route involving a rhodium hydride addition to an olefin derived from the ROH.

  DOI：

  10.1021/om00020a039

文献信息

• The synthesis, properties, and crystal structure of nBu4N[Rh(CO)2(OAc)2], and the exchange of acetate, chloride, and iodide in nBu4N[Rh(CO)2(X)2]
  作者：Anthony Fulford、Neil A. Bailey、Harry Adams、Peter M. Maitlis

  DOI：10.1016/0022-328x(91)80168-j

  日期：1991.10

  Evidence was obtained for the formation of a labile mixed anion [Rh(CO)2I(OAC)]− on reaction of [Rh2(CO)4I2] with nBu4N+ OAc−. It is unlikely that the promotional effect of acetate in methyl acetate carbonylation is due to the participation of acetato-rhodium complexes. Since the lithium acetate reacts readily with iodomethane to give lithium iodide, the observed promotion probably arises from the formation

  的反应Ñ卜4 N [RH）CO）2氯2 ]，1，用CO下醋酸银，得到二乙酸盐Ñ卜4 N [铑（CO）2（OAc）2，2。该配合物已在光谱上表征[ν（CO term）1986，2066; ν（CO 2-单齿）1615cm -1 ]，通过单晶X射线测定。阴离子是平面的，具有单齿乙酸盐，Rh-O 2.074（6）和2.053（7）。配合物2立即与MeI反应生成MeOAc和[Rh（CO）2 I 2 ] -，3，然后通常氧化添加更多的MeI。它还与HCl反应生成HOAC和[Rh（CO）2 Cl 2 ] -。[Rh 2（CO）4 I 2 ]与n Bu 4 N + OAc-反应生成不稳定的混合阴离子[Rh（CO）2 I（OAC）] -的证据。。乙酸盐在乙酸甲酯羰基化中的促进作用不太可能归因于乙酰铑络合物的参与。由于乙酸锂容易与碘甲烷反应生成碘化锂，因此观察到的促进作用可能来自LiI的形成。MeI与n Bu
• Factors influencing the oxidative addition of iodomethane to [Rh(CO)2I2]−, the key step in methanol and methyl acetate carbonylation
  作者：Anthony Fulford、Cathryn E. Hickey、Peter M. Maitlis

  DOI：10.1016/0022-328x(90)85517-3

  日期：1990.11

  The oxidative addition of MeI to A+ [Rh(CO)2I2]− [A = n-Bu4N, Ph4P, and Ph4As], the rate determining step in the Rh and I− catalysed conversion of methanol into acetic acid and of methyl acetate into acetic anhydride, is second order overall, first order in both complex and methyl iodide. The reaction is slower in less polar solvents (k2 1.9 × 10−5 M−1 s−1 in MeOAc, 3.1 × 10−5 in THF, and 10.0 × 10−5

  氧化加入MeI至A +的[Rh（CO）2我2 ] - [A =正丁基4当量，pH 4 P，而Ph 4为]，在Rh和我的速率确定步骤-的催化转化总的来说，甲醇为乙酸，乙酸甲酯为乙酸酐，在络合物和甲基碘中均为一阶。在极性较小的溶剂中反应较慢（在MeOAc中为k 2 1.9×10 -5 M -1 s -1，在THF中为3.1×10 -5，在10.0×10 -5 M -1 s -1在298 K下，在MeOH中）。质子溶剂加速反应；例如加成。3％的水使四氢呋喃中的比率增加四倍。Δ的值G ^ ≠已在MeOH和288和318 K的MeOAc的Δ的值被测量，并且ħ ≠ [60（甲醇），46（的MeOAc）千焦摩尔-1 ]和Δ小号≠ [-120（MeOH）中由它们计算出的，-180（MeOAc）J mol -1 K -1 ]；这些数目非常接近于催化羧化的数目。碘化物也加速了甲基的反应乙酸甲酯高达2倍，对加入20个当量的[我的-];
• Oxidative addition of methyl lodide to dicarbonylrhodium(I) complexes
  作者：Cathryn E. Hickey、Peter M. Maitlis

  DOI：10.1039/c39840001609

  日期：——

  Oxidative addition of Mel to [Rh(CO)2l2]– in aprotic solvents, the ‘rate-determining’ step in the carbonylation of methyl acetate and methyl halides(to acetic anhydride and acyl halides, respectively), is substantially promoted by iodide and bases (L, e.g. 1-methylimidazole).

  将Mel氧化成[Rh（CO）2 l 2 ] –在非质子溶剂中，乙酸甲酯和甲基卤化物（分别为乙酸酐和酰基卤）羰基化的“决定速率”步骤大大促进了碘化物和碱（L，例如1-甲基咪唑）。
• Oxidative addition of RCOI to [AsPh4][Rh(CO)2I2]. Synthesis of [AsPh4][RCORh(CO)2I3] (R = Me, Et, n-Pr, i-Pr)
  作者：Laurie A. Howe、Emilio E. Bunel

  DOI：10.1016/0277-5387(94)00386-s

  日期：1995.1

  Reaction of [AsPh(4)][Rh(CO)(2)I-2] (1) with RCOI yields complexes [AsPhh(4)](2) [RCORh(CO)I-3](2) (2, R = Me; 3, R = Et; 4, R = n-Pr; 5, R= i-Pr). The (CO)-C-13 scram bling process for complexes [AsPh(4)][RCORh((CO)-C-13)(S)I-3] (R = Me, Et; S = CD3CN) along with the skeleton isomerization of [AsPh(4)][RCORh(CO)(S)I-3] (R = n-Pr, i-Pr) was determined by H-1 NMR spectroscopy. Rates of CO insertion into the Rh-C bond in [AsPh(4)][R-Rh(CO)(3)I-3] (R = Me, n-Pr, i-Pr) were determined. Thermolysis of [AsPh(4)] [MeCORh(CO)(CD3CN)I-3] (6) in CD3CN gives methyl iodide in contrast to [AsPh(4)] [i-PrCoRh(Co-13) (CD3CN)I-3] (7) and [AsPh(4)][n-PrCORh((CO)-C-13)(CD3CN)I-3] (8) which give only propene as the organic fragment.
• Oxidative Addition of Alkyl Halides to Rhodium(I) and Iridium(I) Dicarbonyl Diiodides: Key Reactions in the Catalytic Carbonylation of Alcohols
  作者：Paul R. Ellis、Jean M. Pearson、Anthony Haynes、Harry Adams、Neil A. Bailey、Peter M. Maitlis

  DOI：10.1021/om00020a039

  日期：1994.8

  Alkyl iodides (RI) react with [Rh(CO)2I2]- to give acyl species [Rh(CO)(COR)I3]- (R = Et, (n)Pr, (i)Pr) and with [Ir(CO)2]2]- to give alkyl complexes [RIr(CO)2]2]- (R = Et, (n)Pr, (i)Pr, (n)Bu, n-C5H11, n-C6H13). The reactions are analogous to the known reactions of MeI with [Rh(CO)2I2]- and [Ir(CO)2I2]-. The products are characterized spectroscopically and by an X-ray crystal structure determination for Ph4As[(n-C6H13)Ir(CO)2I3] which showed a fac,cis geometry for the anion. [Crystal structure data: monoclinic, a = 9.408(7) angstrom, b = 19.470(16) angstrom, c = 19.529(12) angstrom, beta = 94.99(5)-degrees, Z = 4, space group P2(1)/n (a nonstandard setting of P2(1)/c C2h5, No. 14); 2446 independent reflections (of 5197 measured) for which \F\/sigma(\F\) > 4.0; R = 0.0966 (R(w) = 0.0921, 238 parameters)]. Kinetic data for the reactions of [Rh(CO)2I2]-with EtI. (n)PrI, and (i)PrI and for [Ir(CO)2I2]- with MeI, EtI, and (n)PrI show that oxidative addition of Ri to [M(CO)2I2]- is first-order in both reactants. For M = Rh, reactions showed clean second-order kinetics below 80-degrees-C, though some decomposition occurred at higher temperatures. For M = Ir, clean second-order kinetics were observed with MeI, but reactions with EtI and (n)PrI showed a more complex kinetic behavior. A competing radical pathway is suggested, which can be quenched by added duroquinone. Second-order rate constants, k2, evaluated over the temperature ranges 70-80-degrees-C (M = Rh) and 35-50-degrees-C (M = Ir) gave the following activation parameters: (M = Rh) DELTAH(double dagger)/kJ mol-1 = 50(+/-1) (R = Me), 56(+/-10) (R = Et), 51(+/-10) (R = (n)Pr), 61(+/-15) (R = (i)Pr); DELTAS(double dagger)/J mol-1 K-1 = -165(+/-4) (R = Me), -195(+/-25) (R = Et), -215(+/-25) (R = (n)Pr), -180(+/-30) (R = (i)Pr); (M = Ir) DELTAH(double dagger)/kJ mol-1 = 54(+/-1) (R = Me), 66(+/-5) (R = Et), 66(+/-3) (R = (n)Pr); DELTAS(double dagger)/J mol-1 K-1 -113(+/-4) (R = Me), -123(+/-15) (R = Et), -132(+/-11) (R = (n)Pr). Comparisons are made between the reactions of methyl iodide and the higher alkyl iodides with both [Rh(CO)2I2]-(relative rates: Me, 1000, Et, 3; (n)Pr, 1.7) and [Ir(CO)2I2]- (relative rates: Me, 1000; Et, 2.3; (n)Pr, 0.75). The similarity to reactivity trends for organic nucleophiles suggests an SN2 mechanism, but with a competing radical pathway for iridium. Relative rates for the two nucleophiles, k(Ir)/k(Rh) ca. 150 (R = Me), 220 (R = Et), and 140 (R = (n)Pr), are estimated. Alkyl isomerization (iso --> n) is observed for both [Rh(CO)(COPr)I3]- and (PrIr(CO)2I3]- and displacement of propene from [Rh(CO)(COPr)I3]- by added ethene gives [Rh(CO)(COEt)Is]-reversibly. A mechanism involving hydridoalkene intermediates is proposed. The data are consistent with the carbonylation of the higher alcohols (ROH) proceeding via rate determining oxidative addition of RI to [Rh(CO)2I2]-, rather than by a route involving a rhodium hydride addition to an olefin derived from the ROH.