RhCl{9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene} | 1429191-27-4

• 英文名称: RhCl{9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene}
• 英文别名: RhCl{xant(PⁱPr₂)₂}
• CAS: 1429191-27-4
• 化学式: C₂₇H₄₀ClOP₂Rh
• 分子量: 580.92
• InChiKey: XVLOLZZTKXPWRL-UHFFFAOYSA-M

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：

  RhCl{9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene} 以 苯 为溶剂， 生成
  参考文献：
  名称：

  氯芳烃到POP-铑配合物中的选择性C-Cl键氧化加成

  摘要：

  The C-Cl bond cis oxidative addition of 12 chloroarenes, including chlorobenzene, chlorotoluenes, chlorofluorobenzenes, and di- and trichlorobenzenes to RhH{xant((PPr2)-Pr-i)(2)} (1; xant((PPr2)-Pr-i)(2) = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) and the ability of the resulting rhodium(III) species to undergo reductive elimination reactions are reported. Complex 1 reacts with chlorobenzene to give RhHCl(C6H5){xant((PPr2)-Pr-i)(2)} (2), which eliminates benzene to afford RhCl{xant((PPr2)-Pr-i)(2)} (3). On the other hand, in the presence of potassium tert-butoxide ((KOBu)-Bu-t), it undergoes dehydrodechlorination to yield Rh(C6H5){xant((PPr2)-Pr-i)(2)} (4). The reactions of 1 with 3- and 4-chlorotoluenes lead to RhHCl(C6H4-3-Me){xant((PPr2)-Pr-i)(2)} (5) and RhHCl(C6H4-4-Me){xant((PPr2)-Pr-i)(2)} (6), respectively. Treatment of the acetone solutions of both compounds with. KOtBu also results in their dehydrodechlorination to give Rh(C6H4-3-Me){xant((PPr2)-Pr-i)(2)} (7) and Rh(C6H4-4-Me){xant((PPr2)-Pr-i)(2)} (8). Chlorofluorobenzenes undergo both C-Cl oxidative addition and C-H bond activation in a competitive manner. The amount of the C-H activation product increases as fluorine and chlorine are separated. Complex 1 reacts with o-chlorofluorobenzene to afford the C-Cl oxidative addition product RhHCl(C6H4-2-F){xant((PPr2)-Pr-i)(2)} (9). The reaction of 1 with m-chlorofluorobenzene leads to RhHCl(C6H4-3-F){xant((PPr2)-Pr-i)(2)} (10; 91%) and the C-H bond activation product Rh(C6H3-2-Cl-6-F){xant((PPr2)-Pr-i)(2)} (12; 9%), whereas p-chlorofluorobenzene gives a mixture of RhHCl(C6H4-4-F){xant((PPr2)-Pr-i)(2)} (13; 61%) and Rh(C6H3-3-Cl-6-F){xant((PPr2)-Pr-i)(2)} (15; 39%). The addition of (KOBu)-Bu-t to the acetone solutions of 9, 10, and 13 produces the HCl abstraction and the formation of Rh(C6H4-2-F){xant((PPr2)-Pr-i)(2)} (16), Rh(C6H4-3-F){xant((PPr2)-Pr-i)(2)} (17), and Rh(C6H4-4-F){xant((PPr2)-Pr-i)(2)} (18). In contrast to o-chlorofluorobenzene, 1,2-dichlorobenzene reacts with 1 to give RhHCl(C6H4-2-Cl){xant((PPr2)-Pr-i)(2)} (19; 32%), Rh(C(6)H(4)2-Cl){xant((PPr2)-Pr-i)(2)} (20; 51%) and Rh(C6H3-2,3-Cl-2){xant((PPr2)-Pr-i)(2)} (22; 17%).The reactions of 1 with 1,3- and 1,4-dichlorobenzene lead to the respective C-Cl bond oxidative addition products RhHCl(C6H4-3-Cl){xant((PPr2)-Pr-i)(2)} (23) and RhHCl(C6H4-4-Cl){xant((PPr2)-Pr-i)(2)} (24), which afford Rh(C6H4-3-Cl){xant((PPr2)-Pr-i)(2)} (25) and Rh(C6H4-4-Cl){xant((PPr2)-Pr-i)(2)} (26) by dehydrodechlorination with (KOBu)-Bu-t in acetone. Treatment of 1 with 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes leads to RhHCl(C6H3-2,3-Cl-2){xant((PPr2)-Pr-i)(2)} (27), RhHCl(C6H3-3,4-Cl-2){xant((PPr2)-Pr-i)(2)} (28), and RhHCl(C6H3-3,5-Cl-2){xant((PPr2)-Pr-i)(2)} (29). The addition of (KOBu)-Bu-t to acetone solutions of 27-29 affords 22, Rh(C6H3-3,4-Cl-2){xant((PPr2)-Pr-i)(2)} (30) and Rh(C6H3-3,5-Cl-2){xant((PPr2)-Pr-i)(2)} (31).

  DOI：

  10.1021/acs.organomet.6b00615
• 作为产物：
  描述：

  以 丙酮 为溶剂， 反应 168.0h， 生成 RhCl{9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene}
  参考文献：
  名称：

  氯芳烃到POP-铑配合物中的选择性C-Cl键氧化加成

  摘要：

  The C-Cl bond cis oxidative addition of 12 chloroarenes, including chlorobenzene, chlorotoluenes, chlorofluorobenzenes, and di- and trichlorobenzenes to RhH{xant((PPr2)-Pr-i)(2)} (1; xant((PPr2)-Pr-i)(2) = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) and the ability of the resulting rhodium(III) species to undergo reductive elimination reactions are reported. Complex 1 reacts with chlorobenzene to give RhHCl(C6H5){xant((PPr2)-Pr-i)(2)} (2), which eliminates benzene to afford RhCl{xant((PPr2)-Pr-i)(2)} (3). On the other hand, in the presence of potassium tert-butoxide ((KOBu)-Bu-t), it undergoes dehydrodechlorination to yield Rh(C6H5){xant((PPr2)-Pr-i)(2)} (4). The reactions of 1 with 3- and 4-chlorotoluenes lead to RhHCl(C6H4-3-Me){xant((PPr2)-Pr-i)(2)} (5) and RhHCl(C6H4-4-Me){xant((PPr2)-Pr-i)(2)} (6), respectively. Treatment of the acetone solutions of both compounds with. KOtBu also results in their dehydrodechlorination to give Rh(C6H4-3-Me){xant((PPr2)-Pr-i)(2)} (7) and Rh(C6H4-4-Me){xant((PPr2)-Pr-i)(2)} (8). Chlorofluorobenzenes undergo both C-Cl oxidative addition and C-H bond activation in a competitive manner. The amount of the C-H activation product increases as fluorine and chlorine are separated. Complex 1 reacts with o-chlorofluorobenzene to afford the C-Cl oxidative addition product RhHCl(C6H4-2-F){xant((PPr2)-Pr-i)(2)} (9). The reaction of 1 with m-chlorofluorobenzene leads to RhHCl(C6H4-3-F){xant((PPr2)-Pr-i)(2)} (10; 91%) and the C-H bond activation product Rh(C6H3-2-Cl-6-F){xant((PPr2)-Pr-i)(2)} (12; 9%), whereas p-chlorofluorobenzene gives a mixture of RhHCl(C6H4-4-F){xant((PPr2)-Pr-i)(2)} (13; 61%) and Rh(C6H3-3-Cl-6-F){xant((PPr2)-Pr-i)(2)} (15; 39%). The addition of (KOBu)-Bu-t to the acetone solutions of 9, 10, and 13 produces the HCl abstraction and the formation of Rh(C6H4-2-F){xant((PPr2)-Pr-i)(2)} (16), Rh(C6H4-3-F){xant((PPr2)-Pr-i)(2)} (17), and Rh(C6H4-4-F){xant((PPr2)-Pr-i)(2)} (18). In contrast to o-chlorofluorobenzene, 1,2-dichlorobenzene reacts with 1 to give RhHCl(C6H4-2-Cl){xant((PPr2)-Pr-i)(2)} (19; 32%), Rh(C(6)H(4)2-Cl){xant((PPr2)-Pr-i)(2)} (20; 51%) and Rh(C6H3-2,3-Cl-2){xant((PPr2)-Pr-i)(2)} (22; 17%).The reactions of 1 with 1,3- and 1,4-dichlorobenzene lead to the respective C-Cl bond oxidative addition products RhHCl(C6H4-3-Cl){xant((PPr2)-Pr-i)(2)} (23) and RhHCl(C6H4-4-Cl){xant((PPr2)-Pr-i)(2)} (24), which afford Rh(C6H4-3-Cl){xant((PPr2)-Pr-i)(2)} (25) and Rh(C6H4-4-Cl){xant((PPr2)-Pr-i)(2)} (26) by dehydrodechlorination with (KOBu)-Bu-t in acetone. Treatment of 1 with 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes leads to RhHCl(C6H3-2,3-Cl-2){xant((PPr2)-Pr-i)(2)} (27), RhHCl(C6H3-3,4-Cl-2){xant((PPr2)-Pr-i)(2)} (28), and RhHCl(C6H3-3,5-Cl-2){xant((PPr2)-Pr-i)(2)} (29). The addition of (KOBu)-Bu-t to acetone solutions of 27-29 affords 22, Rh(C6H3-3,4-Cl-2){xant((PPr2)-Pr-i)(2)} (30) and Rh(C6H3-3,5-Cl-2){xant((PPr2)-Pr-i)(2)} (31).

  DOI：

  10.1021/acs.organomet.6b00615
• 作为试剂：
  描述：

  氯代环己烷 在 RhCl{9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene} 、 sodium formate 作用下， 以 异丙醇 为溶剂， 反应 24.0h， 生成 环己烷
  参考文献：
  名称：

  POP-Piner铑（I）配合物促进C（sp3）–Cl键活化

  摘要：

  络合物[的RhCl（κ 3 P，ø，P - {xant（P我镨2）2 }）]（1 ; xant（P我镨2）2 = 9,9-二甲基-4,5-双（二异丙基）the吨）激活一氯和二氯烷烃的C（sp 3）-Cl键，并催化氯烷烃的脱卤作用和苄基氯的均偶联作用。复杂1起反应以氯环己烷，得到[RhHCl 2（κ 3 P，ø，P - {xant（P我镨2）2}）]（2）和环己烯，并使用甲酸钠的2-丙醇溶液作为还原剂，促进氯环烷烃脱卤为环己烷。氧化加成的苄基氯，以1所导致的[Rh（CH 2 PH）氯2（κ 3 P，ø，P - {xant（P我镨2）2 }）]（4）。在1的存在下，用甲酸钠的2-丙醇溶液将该氯代烷烃脱卤，得到甲苯和1，2-二苯乙烷。后者是用KOH而不是甲酸钠选择性地形成的。综合大楼1还可与反式-1,2-二氯环己烷和二氯甲烷反应。与前者反应得到[的RhCl 3（κ 3 P，ø，P - {xant（P我镨2）2

  DOI：

  10.1021/acs.organomet.9b00409

文献信息

• Xantphos-Type Complexes of Group 9: Rhodium versus Iridium
  作者：Miguel A. Esteruelas、Montserrat Oliván、Andrea Vélez

  DOI：10.1021/ic4002658

  日期：2013.5.6

  IrH3xant(PiPr2)2} (5), respectively. In n-octane at 60 °C, complex 2 is stable. However, compound 3 activates the alkane to give the cis-dihydride IrH2Clxant(PiPr2)2} (6) and a mixture of 3- and 4-octene. Complex 6 can be also obtained by the reaction of 3 with H2. Under the same conditions, 2 affords the rhodium analogue RhH2Clxant(PiPr2)2} (7). Compounds 2–4 react with triflic acid (HOTf) to give RhHCl(OTf)xant(PiPr2)2}

  用9,9-二甲基-4,5-双（二异丙基膦基）氧杂蒽[xant（P i Pr 2）2 ]引线处理二聚体[Rh（μ-Cl）（C 8 H 14）2 ] 2（1a）到d 8方平面复合体RhCl xant（P i Pr 2）2 }（2），而铱对应物[Ir（μ-Cl）（C 8 H 14）2 ] 2（1b）的反应给出d 6八面体化合物I rHCl xant（P i Pr 2）[我PrPCH（ME）C ħ 2 ]}（3）作为分子内C-H键活化的膦的异丙基取代基之一的结果。在2-丙醇的0.5 N KOH溶液中搅拌2和3会形成氢化物RhH xant（P i Pr 2）2 }（4）和IrH 3 xant（P i Pr 2）2 }（5） ， 分别。在60°C的正辛烷中，配合物2是稳定的。但是，化合物3会活化烷烃，从而产生顺式-二氢化物IrH 2 Cl xant（P i Pr 2）2 }（6）和3-和4-辛烯的混合物。配合物6也可以通过3与H
• Conclusive Evidence on the Mechanism of the Rhodium-Mediated Decyanative Borylation
  作者：Miguel A. Esteruelas、Montserrat Oliván、Andrea Vélez

  DOI：10.1021/jacs.5b07357

  日期：2015.9.30

  RhClxant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin)xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin)xant(P(i)Pr2)2} (2). The reaction

  已经进行了在铑介导的脱氰硼酸化机制中提出的化学计量反应，并分离和表征了所有相关中间体，包括它们的 X 射线结构。复合物 RhClxant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) 与双(频哪醇)二硼反应 ( B2pin2)，在苯中，得到铑 (III) 衍生物 RhHCl(Bpin)xant(P(i)Pr2)2} (4) 和 PhBpin。该反应涉及 B2pin2 与 1 的氧化加成以得到 RhCl(Bpin)2xant(P(i)Pr2)2}，这消除了 ClBpin 生成 Rh(Bpin)xant(P(i)Pr2)2} (2 ）。后者与溶剂的反应产生 PhBpin 和一氢化物 RhHxant(P(i)Pr2)2} (6)，这增加了消除的 ClBpin。配合物
• POP-Pincer Silyl Complexes of Group 9: Rhodium versus Iridium
  作者：Miguel A. Esteruelas、Montserrat Oliván、Andrea Vélez

  DOI：10.1021/ic401931y

  日期：2013.10.21

  Rh(SiClPh2)xant(PiPr2)2} (7), whereas the iridium derivative 5 gives IrH2(SiClPh2)xant(PiPr2)2} (9), which is stable. In agreement with the formation of 7, the reactions of 8 with silanes are a general method to prepare square planar d8-rhodium-silyl derivatives. Thus, the addition of triethylsilane and triphenylsilane to 8 initially leads to the dihydrides RhH2(SiR3)xant(PiPr2)2} (SiR3 = SiEt3 (10)

  9,9-二甲基-4,5-双（二异丙基膦基）x吨（xant（P i Pr 2）2）衍生物RhCl xant（P i Pr 2）2 }（1）和I rHCl xant（P i Pr 2））[ i PrPCH（Me）CH 2 ]}（2）与二苯基硅烷和三乙基硅烷反应，得到饱和的d 6-化合物RhHCl（SiR 3）xant（P i Pr 2）2 }（SiR 3 = SiHPh 2（3），SiEt 3（4））和IrHCl（SiR 3）xant（P i Pr 2）2 }（SiR 3＝ SiHPh 2（5），SiEt 3（6））。配合物3和5通过MH xant（P i Pr 2）2 }（M = Rh（8），Ir（E））中间体经历Cl / H位置交换过程。铑配合物3提供了方形的平面d 8-甲硅烷基衍生物Rh（SiClPh 2）xant（P i Pr 2）2 }（7），而铱衍生物5得到稳定的IrH
• C–Cl Oxidative Addition and C–C Reductive Elimination Reactions in the Context of the Rhodium-Promoted Direct Arylation
  作者：Laura A. de las Heras、Miguel A. Esteruelas、Montserrat Oliván、Enrique Oñate

  DOI：10.1021/acs.organomet.1c00643

  日期：2022.3.28

  defining the direct arylation promoted by a redox-pair Rh(I)–Rh(III) is reported. Starting from the rhodium(I)-aryl complex RhPhκ3-P,O,P-[xant(PiPr2)2]} (xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene), the reactions include C–Cl oxidative addition of organic chlorides, halide abstraction from the resulting six-coordinate rhodium(III) derivatives, C–C reductive coupling between the initial

  报道了由氧化还原对 Rh(I)–Rh(III) 促进的化学计量元素反应循环，该反应定义了直接芳基化。从铑(I)-芳基络合物RhPhκ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (xant(P i Pr 2 ) 2 = 9,9-二甲基-4)开始， 5-双(二异丙基膦)呫吨)，反应包括有机氯化物的C-Cl氧化加成、从所得六配位铑(III)衍生物中提取卤化物、初始芳基配体与添加的有机基团之间的C-C还原偶联，新芳烃的 C-H 键的氧化加成，以及生成的氢化物-铑(III)-芳基物质的去质子化，形成新的铑(I)-芳基衍生物。在这种情况下，2-氯吡啶、氯苯、氯化苄和二氯甲烷氧化加成到 RhPhκ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} 和 C–C 的动力学从 [RhPh 2 κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]}]BF 4和 [RhPh(CH