trans-[RhCl(=C=CHC(OH)Ph(C6H4Me-o))((i-Pr)2AsCH2CH2OMe)2] | 162443-27-8

• 英文名称: trans-[RhCl(=C=CHC(OH)Ph(C6H4Me-o))((i-Pr)2AsCH2CH2OMe)2]
• CAS: 162443-27-8
• 化学式: C₃₄H₅₆As₂ClO₃Rh
• 分子量: 801.019
• InChiKey: LMAOSMNHVKPXJE-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：

  trans-[RhCl(=C=CHC(OH)Ph(C6H4Me-o))((i-Pr)2AsCH2CH2OMe)2] 在 aluminum oxide 作用下， 以 正己烷 为溶剂， 以89%的产率得到trans-[RhCl(=C=C=CPh(C6H4Me-o))((i-Pr)2AsCH2CH2OMe)2]
  参考文献：
  名称：

  A series of rhodium(I) complexes, including carbene, vinylidene and allenylidene derivatives, with the bifunctional arsine Pri 2AsCH2CH2OMe as ligand

  摘要：

  A series of rhodium(I) complexes containing the new bifunctional arsine ligand Pr(2)(i)AsCH(2)CH(2)OMe I has been prepared. Most of the compounds were obtained from the ethene derivative trans-(RhCl(C2H4) ((Pr2AsCH2CH)-As-i(2)OMe)(2)} 5 which was obtained from [{RhCl(C2H4)(2)}(2)] and I in about 80% yield. The ethene can be displaced by CO, CNBUt, CH2=CHC(O)Me, CH2=CHCO(2)Me, HC=CPh, HC=CCO(2)Me, PhC=CSiMe(3), MeC=CMe, PhC=CMe, MeC=CC=CMe or Me(3)SiC=CC=CSiMe(3) (L) to give the four-co-ordinated rhodium(I) complexes trans-[RhCl(L)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] almost quantitatively. The reaction of 5 with H-2 affords the dihydride {RhH2Cl(Pr(2)(i)AsCH(2)CH(2)OMe)(2)} which appears to be fluxional in solution. Photolysis of 5 leads to the elimination of CH2=CHOMe and the formation of trans-[RhCl(C2H4) (HAsPr2i)(2)] which is also accessible from 3 and HAsPr2i. The vinylidene complexes trans-[RhCl(=C=CHR)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] are obtained either on photochemically induced rearrangement of the isomeric alk-1-yne derivatives (R = Ph or CO(2)Me) or directly from 5 and HC=CR (R = Me or Bu(t)). The reaction of 5 with a large excess of HC=CMe or MeC=CBu(t) gives the rhodium(i) allenes trans-[RhCl(CH2=C=CHR) (Pr(2)(i)AsCH(2)CH(2)OMe)(2)] (R = H or Bu(t)). The allenylidene compounds trans-[RhCl(=C=C=CRR') (Pr(2)(i)AsCH(2)CH(2)OMe)(2)] (R = Ph, R' = Ph or C(6)H(4)Me-o) are obtained from the functionalized vinylidene derivatives trans-[RhCl(=C=CHCRR'OH)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] upon treatment with Al2O3. From trans-[RhCl(=C=C=CRR')(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] and NaC5H5 the half-sandwiches [C5H5Rh(=C=C=CRR')(Pr(2)(i)AsCH(2)CH(2)OMe)] have been prepared. Compound 5 reacts with N(2)CPh(2) and N2C(C(6)H(4)Me-p)(2) to yield the carbene complexes trans-[RhCl(=CR(2))(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] whereas from 5 and N(2)CRC(O)Ph (R = H or Ph) the diazoalkane rhodium compounds trans-[RhCl{N(2)CRC(O)Ph}(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] are obtained.

  DOI：

  10.1039/dt9940003415
• 作为产物：
  描述：

  trans-[RhCl(C2H4)((i-Pr)2AsCH2CH2OMe)2] 、 1-phenyl-1-(o-tolyl)prop-2-yn-1-ol 以 甲苯 、 正戊烷 为溶剂， 以86%的产率得到trans-[RhCl(=C=CHC(OH)Ph(C6H4Me-o))((i-Pr)2AsCH2CH2OMe)2]
  参考文献：
  名称：

  A series of rhodium(I) complexes, including carbene, vinylidene and allenylidene derivatives, with the bifunctional arsine Pri 2AsCH2CH2OMe as ligand

  摘要：

  A series of rhodium(I) complexes containing the new bifunctional arsine ligand Pr(2)(i)AsCH(2)CH(2)OMe I has been prepared. Most of the compounds were obtained from the ethene derivative trans-(RhCl(C2H4) ((Pr2AsCH2CH)-As-i(2)OMe)(2)} 5 which was obtained from [{RhCl(C2H4)(2)}(2)] and I in about 80% yield. The ethene can be displaced by CO, CNBUt, CH2=CHC(O)Me, CH2=CHCO(2)Me, HC=CPh, HC=CCO(2)Me, PhC=CSiMe(3), MeC=CMe, PhC=CMe, MeC=CC=CMe or Me(3)SiC=CC=CSiMe(3) (L) to give the four-co-ordinated rhodium(I) complexes trans-[RhCl(L)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] almost quantitatively. The reaction of 5 with H-2 affords the dihydride {RhH2Cl(Pr(2)(i)AsCH(2)CH(2)OMe)(2)} which appears to be fluxional in solution. Photolysis of 5 leads to the elimination of CH2=CHOMe and the formation of trans-[RhCl(C2H4) (HAsPr2i)(2)] which is also accessible from 3 and HAsPr2i. The vinylidene complexes trans-[RhCl(=C=CHR)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] are obtained either on photochemically induced rearrangement of the isomeric alk-1-yne derivatives (R = Ph or CO(2)Me) or directly from 5 and HC=CR (R = Me or Bu(t)). The reaction of 5 with a large excess of HC=CMe or MeC=CBu(t) gives the rhodium(i) allenes trans-[RhCl(CH2=C=CHR) (Pr(2)(i)AsCH(2)CH(2)OMe)(2)] (R = H or Bu(t)). The allenylidene compounds trans-[RhCl(=C=C=CRR') (Pr(2)(i)AsCH(2)CH(2)OMe)(2)] (R = Ph, R' = Ph or C(6)H(4)Me-o) are obtained from the functionalized vinylidene derivatives trans-[RhCl(=C=CHCRR'OH)(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] upon treatment with Al2O3. From trans-[RhCl(=C=C=CRR')(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] and NaC5H5 the half-sandwiches [C5H5Rh(=C=C=CRR')(Pr(2)(i)AsCH(2)CH(2)OMe)] have been prepared. Compound 5 reacts with N(2)CPh(2) and N2C(C(6)H(4)Me-p)(2) to yield the carbene complexes trans-[RhCl(=CR(2))(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] whereas from 5 and N(2)CRC(O)Ph (R = H or Ph) the diazoalkane rhodium compounds trans-[RhCl{N(2)CRC(O)Ph}(Pr(2)(i)AsCH(2)CH(2)OMe)(2)] are obtained.

  DOI：

  10.1039/dt9940003415