| 161205-32-9

• CAS: 161205-32-9
• 化学式: CF₃O₃S*C₅₅H₄₆O₄OsP₄Rh
• 分子量: 1337.04
• InChiKey: GQDTVYOPAVNGPM-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：

  、 以 正己烷 、 二氯甲烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Heterobinuclear Hydrido, Alkyl, and Related Complexes of Rh/Os. Site-Specific Reductive Elimination of Methane from a Rh/Os Core and the Structures of [RhOs(CH2CN)(CO)3(dppm)2] and [RhOs(CH3)(CO)3(dppm)2]

  摘要：

  This paper reports the synthesis and characterization of a series of hydride, alkyl, alkenyl, and related heterobimetallic complexes of Rh and Os and the site-specific reductive elimination of methane from hydride methyl complexes. Reaction of [RhOs(CO)(3)(NCMe)(mu-H)(dppm)(2)](2+) (3, dppm = Ph(2)PCH(2)PPh(2)) with NaC=CH in acetonitrile yields the acetylide complex [RhOs(C2H)(CO)(3)(dppm)(2)] (6)and the cyanomethyl complex [RhOs(CH2-CN)(CO)(3)(dppm)(2)] (7). The same reaction under CO instead results in deprotonation of one dppm group to give [Rhos(CO)(4)(dppm-H)(dppm)] (8, dppm-H = bis(diphenylphosphino)methanide). The methanide carbon can be alkylated to give [RhOs(CO)(4)(Ph(2)PCH(CH3)PPh(2))(dppm)](+) (9) or protonated to give the known compound [RhOs(CO)(4)(dppm)(2)](+)(2). The methyl complex [RhOs(CH3)(CO)(3)(dppm)(2)] (10) is prepared by several routes, and upon protonation yields [RhOs(CO)(3)(mu-H)(mu(2)-eta(3)-(o-C6H4)PhPCH(2)PPh(2))(dppm)](+) (14) via methane loss. If the reaction is carried out at -80 degrees C and slowly warmed, three hydride methyl intermediates are observed at different temperatures, yielding information about the reductive elimination from these heterobinuclear species, which appears to occur from the Os center. An alkenyl complex analogous to the alkyl species 7 and 10 can be obtained by the reaction,of [RhOsH(CO)(3)(dppm)(2)] (1) with dimethyl acetylenedicarboxylate resulting in insertion into the Os-Il bond and migration of the resulting alkenyl group to Rh yielding [RhOs(MeO(2)CC=C(H)CO(2)Me)(CO)(3)(dppm)(2)] (18). Protonation of 18 yields [RhOs(R)(CO)(3)(mu-H)(dppm)(2)](+) (19) and alkylation yields [RhOs(R)(CH3)(CO)(3)(dppm)(2)](+) (20, R = MeO(2)CC=C(H)CO(2)Me). Compound 20 has the vinylic moiety bound to Rh with the methyl group on Os. The structures of 7 and 10 have been established by X-ray crystallography. Compound 7 crystallizes in the monoclinic space group C2/c with a = 18.313(3) Angstrom, b = 13.279(2) Angstrom, c = 22.492(5) Angstrom, beta = 115.89(1)degrees, and Z = 4; compound 10 crystallizes in the triclinic space group P1 with a = 11.102(2) Angstrom, b = 11.684(3) Angstrom, c = 10.954(3) Angstrom, alpha = 111.79(2)degrees, beta = 93.16(2)degrees, gamma = 68.18(2)degrees, and Z = 1. Both compounds are disordered at an inversion center, although only the metals and the carbonyl and alkyl groups are disordered. Both models refined acceptably: R = 0.046, R(w) = 0.058 (7); R = 0.047, R(w) = 0.077 (10). The geometries of the two complexes are almost identical, having the cyanomethyl or methyl group terminally bound to Rh and having the three carbonyls on Os. One carbonyl forms a semibridging interaction with Rh.

  DOI：

  10.1021/ja00106a028
• 作为产物：
  描述：

  [RhOs(CO)4(dppm)2][BF4] 在 C₄H₉Li 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  Heterobinuclear Hydrido, Alkyl, and Related Complexes of Rh/Os. Site-Specific Reductive Elimination of Methane from a Rh/Os Core and the Structures of [RhOs(CH2CN)(CO)3(dppm)2] and [RhOs(CH3)(CO)3(dppm)2]

  摘要：

  This paper reports the synthesis and characterization of a series of hydride, alkyl, alkenyl, and related heterobimetallic complexes of Rh and Os and the site-specific reductive elimination of methane from hydride methyl complexes. Reaction of [RhOs(CO)(3)(NCMe)(mu-H)(dppm)(2)](2+) (3, dppm = Ph(2)PCH(2)PPh(2)) with NaC=CH in acetonitrile yields the acetylide complex [RhOs(C2H)(CO)(3)(dppm)(2)] (6)and the cyanomethyl complex [RhOs(CH2-CN)(CO)(3)(dppm)(2)] (7). The same reaction under CO instead results in deprotonation of one dppm group to give [Rhos(CO)(4)(dppm-H)(dppm)] (8, dppm-H = bis(diphenylphosphino)methanide). The methanide carbon can be alkylated to give [RhOs(CO)(4)(Ph(2)PCH(CH3)PPh(2))(dppm)](+) (9) or protonated to give the known compound [RhOs(CO)(4)(dppm)(2)](+)(2). The methyl complex [RhOs(CH3)(CO)(3)(dppm)(2)] (10) is prepared by several routes, and upon protonation yields [RhOs(CO)(3)(mu-H)(mu(2)-eta(3)-(o-C6H4)PhPCH(2)PPh(2))(dppm)](+) (14) via methane loss. If the reaction is carried out at -80 degrees C and slowly warmed, three hydride methyl intermediates are observed at different temperatures, yielding information about the reductive elimination from these heterobinuclear species, which appears to occur from the Os center. An alkenyl complex analogous to the alkyl species 7 and 10 can be obtained by the reaction,of [RhOsH(CO)(3)(dppm)(2)] (1) with dimethyl acetylenedicarboxylate resulting in insertion into the Os-Il bond and migration of the resulting alkenyl group to Rh yielding [RhOs(MeO(2)CC=C(H)CO(2)Me)(CO)(3)(dppm)(2)] (18). Protonation of 18 yields [RhOs(R)(CO)(3)(mu-H)(dppm)(2)](+) (19) and alkylation yields [RhOs(R)(CH3)(CO)(3)(dppm)(2)](+) (20, R = MeO(2)CC=C(H)CO(2)Me). Compound 20 has the vinylic moiety bound to Rh with the methyl group on Os. The structures of 7 and 10 have been established by X-ray crystallography. Compound 7 crystallizes in the monoclinic space group C2/c with a = 18.313(3) Angstrom, b = 13.279(2) Angstrom, c = 22.492(5) Angstrom, beta = 115.89(1)degrees, and Z = 4; compound 10 crystallizes in the triclinic space group P1 with a = 11.102(2) Angstrom, b = 11.684(3) Angstrom, c = 10.954(3) Angstrom, alpha = 111.79(2)degrees, beta = 93.16(2)degrees, gamma = 68.18(2)degrees, and Z = 1. Both compounds are disordered at an inversion center, although only the metals and the carbonyl and alkyl groups are disordered. Both models refined acceptably: R = 0.046, R(w) = 0.058 (7); R = 0.047, R(w) = 0.077 (10). The geometries of the two complexes are almost identical, having the cyanomethyl or methyl group terminally bound to Rh and having the three carbonyls on Os. One carbonyl forms a semibridging interaction with Rh.

  DOI：

  10.1021/ja00106a028