[RhOs(CO)4(dppm)2][BF4] | 131178-41-1

• 英文名称: [RhOs(CO)4(dppm)2][BF4]
• CAS: 131178-41-1
• 化学式: BF₄*C₅₄H₄₄O₄OsP₄Rh
• 分子量: 1260.75
• InChiKey: PZHBTLFCWFCALZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  [RhOs(CO)4(dppm)2][BF4] 在 C₄H₉Li 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 以47%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)3(μ-H)2(μ-Ph2PCH2PPh2)2][BF4] 在 CO 作用下， 以 二氯甲烷 为溶剂， 以93%的产率得到[RhOs(CO)4(dppm)2][BF4]
  参考文献：
  名称：

  铑和的低价杂双核络合物。配位不饱和铑中心对反应活性的影响

  摘要：

  The coordinatively unsaturated complex [RhOsH(CO)3(dppm)2] (1) is converted smoothly to the chloro analogue [RhOsCl(CO)3(dppm)2] (2) in carbon tetrachloride. Compound 1 also reacts with the electrophiles HBF4.Et2O and [AuPPh3][BF4], yielding [RhOs(CO)3(mu-H)(mu-X)(dppm)2][BF4] (X = H (3), AuPPh3 (4)). The bridging AuPPh3 group is readily replaced by an iodo group in the reaction of 4 with I2, yielding [RhOs(CO)3(mu-H)(mu-I)(dppm)2][BF4] (5). Reductive elimination of H2 from 3, in the presence of carbon monoxide, is reversible and yields [RhOs(CO)4(dppm)2][BF4] (6), which also reacts with the above electrophiles, yielding [RhOs(CO)4(mu-X)(dppm)2][BF4]2 (X = H (7), AuPPh3 (8)). Reaction of 6 with (t)BuNC leads to substitution of the carbonyl on Os that is trans to the Rh-Os bond to give [RhOs(CO)3-((t)BuNC)(dppm)2][BF4] (9). Compound 6 also reacts with the alkynes dimethyl acetylenedicarboxylate (DMAD) and hexafluoro-2-butyne (HFB) to give the alkyne-bridged products [RhOs(CO)3(mu-CO)(mu-DMAD)(dppm)2][BF4] (11) and [RhOs(CO)3(mu-HFB)(dppm)2][BF4] (13), respectively. Carbonyl loss from 11 occurs under mild conditions to yield [RhOs(CO)3(mu-DMAD)(dppm)2][BF4] (12), analogous to compound 13. This carbonyl loss is facilitated by donation of a pair of electrons from Rh to Os with formation of a Rh-->Os dative bond. Addition of anionic or neutral ligands (L) to compound 12 yields the species [RhOs(CO)2L(mu-CO)(mu-DMAD)(dppm)2]n+ (n = 0, 1, respectively), in which L is coordinated on Rh and the original Rh-bound carbonyl has moved to the bridging site. Neutral ligands such as isocyanides react with 13 to yield products analogous to those obtained with 12; however, the I- and S2PMe2- anions (X-) react with 12 with accompanying CO loss to yield [RhOsX(CO)2(mu-HFB)(dppm)2], in which X is bound to Rh with both carbonyls on Os. The other alkyne-bridged dicarbonyls [RhOs(CO)2L(mu-RC = CR)(dppm)2]n+ can also be obtained by heating the tricarbonyl precursors. The structure of compound 12 has been determined by X-ray techniques. This compound crystallizes with two CH2Cl2 molecules in the triclinic space group P1BAR with a = 14.811 (2) angstrom, b = 19.250 (3) angstrom, c = 11.611 (1) angstrom, alpha = 103.27 (1)-degrees, beta = 94.26 (1)-degrees, gamma = 87.74 (1)-degrees, V = 3212 (2) angstrom-3, and Z = 2. Refinement has converged at R = 0.041 and R(w) = 0.060 on the basis of 9594 unique observations and 512 parameters varied. The geometry about Rh is essentially square planar, ignoring the Rh-Os interaction, whereas that about Os is a distorted octahedron when the dative Rh-->Os interaction is taken into account. The Rh-Os separation of 2.8744 (3) angstrom is consistent with a single bond.

  DOI：

  10.1021/om00047a065

文献信息

• Methylene-to-Acetyl Conversion in Heterobinuclear Rh/Os Complexes:  Models for Oxygenate Formation by Bimetallic Fischer−Tropsch Catalysts
  作者：Steven J. Trepanier、Robert McDonald、Martin Cowie

  DOI：10.1021/om030282m

  日期：2003.6.1

  Protonation of the methylene-bridged complex [RhOs(CO)(3)(mu-CH2)(mu-CO)(dppm)(2)][CF3SO3] with triflic acid at -80 degreesC yields the methyl complex [RhOs(CO)(3)(mu-CH2)(dppm)(2)] [CF3SO3] (1) in which the methyl group is primarily bound to Os while involved in an agostic interaction with Rh. Warming this species to -20 degreesC results in methyl migration to a terminal site on Rh, yielding [RhOs(CH3)(CO)(2)(mu-CO)(2)(dppm)(2)] [CF3SO3](2) (2), and subsequent warming to ambient temperature results in migratory insertion to yield the acetyl-bridged [RhOs(CF3SO3)(CO)(2)(mu-C(CH3)O)(mu-CO)(dppm)(2)] [CF3SO3] (3). Replacement of the coordinated triflate anion in 3 by CO and PMe3 occurs at low temperature to give [RhOs(L)(CO)(2)(mu-C(CH3)O)(mu-CO)(dppm)(2)] [CF3SO3](2) (L = CO (4), PMe3 (5a)). Warming the PMe3 adduct results in transformation of the acetyl group, which is C-bound to Rh in 5a, to a group that is C-bound to Os in 5b. One carbonyl in 3 is labile and is readily lost, yielding [RhOs(CF3SO3)(CO)(2)(mu-C(CH3)O)(dppm)(2)] [CF3SO3] (6). Attempts to obtain the above methyl or acetyl species by reaction of the hydride-bridged species [RhOs(X)(CO)(3)(mu-H)(mu-CO)(dppm)(2)] [X] (X = CF3SO3 (7a), BF4 (7b)) with diazomethane were unsuccessful.