Rh(CO)Cl((o-methoxyphenyl)diphenylphosphane)2 | 323202-46-6

• 英文名称: Rh(CO)Cl((o-methoxyphenyl)diphenylphosphane)2
• 英文别名: trans-[Rh(CO)Cl(η1-P-Ph2PC6H4-2-OCH3)2]
• CAS: 323202-46-6
• 化学式: C₃₉H₃₄ClO₃P₂Rh
• 分子量: 751.003
• InChiKey: ZAOHUARYWFUHRL-UHFFFAOYSA-M

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：
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• 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)Cl((o-methoxyphenyl)diphenylphosphane)2 、 碘甲烷 以 二氯甲烷 为溶剂， 生成 [RhCl(COCH3)(I)(η2-P,O-Ph2PC6H4-2-OCH3)2]
  参考文献：
  名称：

  Chelate and trans effect of P,O donor phosphine ligands on rhodium catalyzed carbonylation of methanol

  摘要：

  Four complexes of the type [Rh(CO)Cl(eta(2)-P,O-L)](1a,1b) and [Rh(CO)Cl(eta(1)-P-L)(2)](2a,2b), where L = Ph2PC6H4-2-OCH3(a) and Ph2PC6H4-2-CH2OCH3(b), have been synthesized by the reaction of [Rh(CO)(2)Cl](2) with appropriate mol equivalents of the ligands in CH2Cl2. The complexes show single intense v(CO) bands in the range 1965-1989 cm(-1) indicating the presence of terminal carbonyl groups. All the complexes have been characterized by elemental analyses, mass spectrometry. IR and multinuclear NMR (H-1, P-31 and C-13) spectroscopy, and the molecular structure of the ligand b is determined by single crystal X-ray diffraction. The complexes undergo oxidative addition (OA) with excess CH3I to afford Rh(III)-acyl complexes of the type [RhCl(COCH3)I(L)](3a,3b) and [RhCl(COCH3)I(L)(2)](4a,4b). The kinetic data for the OA reactions with CH3I indicate a first order reaction and also exhibit that the rate of OA for the chelate complexes (1a and 1b) is higher than those of trans-complexes (2a and 2b). The catalytic efficiencies of 1a, 1b, 2a and 2b in carbonylation of methanol exhibit higher Turn Over Frequency (TOF) 689-1808 h(-1) than the well-known Monsanto's species [Rh(CO)(2)I-2](-)(TOF = 464-1000 h(-1)) under similar experimental conditions. The catalytic activities vary in the order as 1a > 1b > 2a > 2b. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2011.10.023
• 作为产物：
  描述：

  对茴香基二苯基膦 、 di(rhodium)tetracarbonyl dichloride 以 二氯甲烷 为溶剂， 以72%的产率得到Rh(CO)Cl((o-methoxyphenyl)diphenylphosphane)2
  参考文献：
  名称：

  Chelate and trans effect of P,O donor phosphine ligands on rhodium catalyzed carbonylation of methanol

  摘要：

  Four complexes of the type [Rh(CO)Cl(eta(2)-P,O-L)](1a,1b) and [Rh(CO)Cl(eta(1)-P-L)(2)](2a,2b), where L = Ph2PC6H4-2-OCH3(a) and Ph2PC6H4-2-CH2OCH3(b), have been synthesized by the reaction of [Rh(CO)(2)Cl](2) with appropriate mol equivalents of the ligands in CH2Cl2. The complexes show single intense v(CO) bands in the range 1965-1989 cm(-1) indicating the presence of terminal carbonyl groups. All the complexes have been characterized by elemental analyses, mass spectrometry. IR and multinuclear NMR (H-1, P-31 and C-13) spectroscopy, and the molecular structure of the ligand b is determined by single crystal X-ray diffraction. The complexes undergo oxidative addition (OA) with excess CH3I to afford Rh(III)-acyl complexes of the type [RhCl(COCH3)I(L)](3a,3b) and [RhCl(COCH3)I(L)(2)](4a,4b). The kinetic data for the OA reactions with CH3I indicate a first order reaction and also exhibit that the rate of OA for the chelate complexes (1a and 1b) is higher than those of trans-complexes (2a and 2b). The catalytic efficiencies of 1a, 1b, 2a and 2b in carbonylation of methanol exhibit higher Turn Over Frequency (TOF) 689-1808 h(-1) than the well-known Monsanto's species [Rh(CO)(2)I-2](-)(TOF = 464-1000 h(-1)) under similar experimental conditions. The catalytic activities vary in the order as 1a > 1b > 2a > 2b. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2011.10.023

文献信息

• Structural and Theoretical Studies ofortho-Substituted Triphenylphosphane Ligands and Their Rhodium(I) Complexes
  作者：Pekka Suomalainen、Sirpa Jääskeläinen、Matti Haukka、Riitta H. Laitinen、Jouni Pursiainen、Tapani A. Pakkanen

  DOI：10.1002/1099-0682(200012)2000:12<2607::aid-ejic2607>3.0.co;2-r

  日期：2000.12