(OC-6-42)-carbonylchloronitrosyl(trifluoromethanesulfonato)bis(trimethyl phosphite)rhenium(I) | 178211-88-6

• 英文名称: (OC-6-42)-carbonylchloronitrosyl(trifluoromethanesulfonato)bis(trimethyl phosphite)rhenium(I)
• CAS: 178211-88-6
• 化学式: C₈H₁₈ClF₃NO₁₁P₂ReS
• 分子量: 676.9
• InChiKey: LLUIBRFDIOLRNL-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  cis,trans-[ReCl2(P(OMe)3)2(CO)(NO)] 、 silver trifluoromethanesulfonate 以 甲苯 为溶剂， 以86%的产率得到(OC-6-42)-carbonylchloronitrosyl(trifluoromethanesulfonato)bis(trimethyl phosphite)rhenium(I)
  参考文献：
  名称：

  The Nitrosyl Ligand and the Rhenium−Triflate Bond in Rhenium(I) Complexes

  摘要：

  The reaction of ReCl(2)L(2)(CO)(NO) (L = P(OMe)(3) (1a), PEt(3) (1b)) with excess silver trifluoromethanesulfonate (AgOTf) in boiling acetonitrile led to an isomeric mixture of [ReCl(CH3CN)(2)L(CO)(NO)][OTf] (L = P(OMe)(3) (2a) PEt(3) (2b)) (approximately 2:1 ratio) with the chloride ligands trans to CO or NO. The isomers of 2a and 2b could not be separated, except for a few yellow prisms of the trans Cl, NO compound of 2b, the structure of which was established by an X-ray diffraction study. The cation of 2b contains an octahedral Re atom bearing one phosphine ligand trans to one acetonitrile molecule (Re-N3 2.144(6) Angstrom). A second acetonitrile ligand (Re-N2 2.143(6) Angstrom) is located trans to the CO ligand (Re-Cl 1.928(8) Angstrom, C1-O2 1.142(10) Angstrom) and the chlorine substituent is arranged trans to the NO group (Re-N1 1.810(3) Angstrom, N1-O1 1.190(11) Angstrom). The Cl-Re-NO moiety was found to be positionally disordered. For further characterization of these isomers by chemical means, 2a and 2b were reacted with bpy to yield stable [ReCl(bpy)(CO)L(NO)][OTf] derivatives (L = P(OMe)(3) (3a), PEt(3) (3b)). The solid state IR spectrum supports the assumption that the isomers of 3a and 3b co-crystallize in the same crystal framework. This apparently prevented separation by crystallization. The reaction of 1 with 1 or 2 equiv of AgOTf in boiling toluene allowed the preparation of the mono- and disubstituted complexes ReCl(OTf)L(2)(CO)(NO) (L = P(OMe)(3) (4a), PEt(3) (4b)) and Re(OTf)(2)L(2)(CO)(NO) (L = P(OMe)(3) (5a), PEt(3) (5b)). The replacement of the triflate ligands in 5a and 5b by acetonitrile are slow reactions (approximately 5d for 5a and 15h for 5b at room temperature), which proceed with retention of the geometry. They result in the formation of the ionic [Re(CH3CN)(2)L(2)(CO)(NO)][OTf](2) products (L = P(OMe)(3) (6a), PEt(3) (6b)). The structure of 6a was confirmed by an X-ray diffraction study. IR and P-31 NMR investigations of the acetonitrile monosubstituted intermediates of this reaction indicated a somewhat faster replacement of the triflate ligand disposed trans to the carbonyl group. In the presence of bpy, 5a underwent in boiling toluene an Arbuzov-like phosphite dealkylation, producing a dinuclear [Re(CO)(bpy)(NO)[P(O)(OMe)(2)]](2)[OTf](2) (7) complex in which the two Re fragments are linked by two phosphonite moieties, forming a planar six-membered ring. The reaction of 5b with bpy gave only decomposition products. By analogy, Re(OTf)(CO)(3)(PEt(3))(2) (8) was prepared and reacted with bpy under the same conditions as for 5b. In this case [Re(CO)(2)(bpy)(PEt(3))(2)][OTf] (9) was isolated demonstrating that the presence of the nitrosyl ligand significantly influences the reactivity of Re-1 complexes. The compounds 2b, 5b, 6a, 7, and 8 were characterized by X-ray analyses. Crystal data follow. C12H21CIF3N3O5PReS (2b): monoclinic, space group P2(1)/c, a = 13.581(6) Angstrom, b = 13.063(5) Angstrom, c = 12.608(5) Angstrom, beta = 93.48(2)degrees, V = 2232.6(16) Angstrom(3), Z = 4. The structure was solved by the Patterson method and refined by full-matrix least squares procedures to R = 0.0441, R(w) = 0.0699 for 4239 observed reflections with \F-o\ greater than or equal to 4 sigma(\F-o\).C14H24F6N3O14P2ReS2 (6a): monoclinic, space group C2/c, a 15.610(4) Angstrom, b = 11.159(3) Angstrom, c = 17.006(4) Angstrom, beta = 91.50(2)degrees, V = 2961.3(12) Angstrom(3), Z = 4. The structure was solved by the Patterson method and refined by full-matrix least squares procedures to R = 0.0541, R(w) = 0.0892 for 3222 observed reflections with \F-o\ greater than or equal to 4 sigma(\F-o\). 5b: triclinic, space group , a = 9.066(2) Angstrom, b = 12.161(3) Angstrom, c = 12.759(3) Angstrom, alpha = 88.01(2)degrees, beta = 82.83(2)degrees, gamma = 86.53(2)degrees, V = 1392.6(6) Angstrom(3), Z = 2. 7: triclinic, space group , a = 9.158(3) Angstrom, b = 10.319(2) Angstrom, c = 14.641(4) Angstrom, alpha = 103.54(2)degrees, beta = 94.16(2)degrees, gamma = 115.75(2)degrees, V = 1187.3(5) Angstrom(3), Z = 1. 8: triclinic, space group <(P)1over bar>, a = 8.287(3) Angstrom, b = 9.672(3) Angstrom, c = 16.429(6) Angstrom, alpha = 94.86(3)degrees, beta = 90.23(3)degrees, gamma = 112.20(2)degrees, V = 1214.0(7) Angstrom(3), Z = 2.

  DOI：

  10.1021/ic9510829