Reaction of 2,2'-bipyridine (bpy) with dirhodium carboxylates: mono-bpy products with variable chelate binding modes and insights into the reaction mechanism Academic Article uri icon

abstract

  • Synthetic procedures are described for the preparation of mono-2,2′-bipyridine (bpy) complexes possessing the Rh24+ core. Reaction of Rh2(OAc)4(MeOH)2 (1) with 1 equiv of bpy in Me2CO produces Rh2(OAc)4(bpy) (3) in excellent yield. The compound crystallizes in the triclinic space group P1̄ with the following cell parameters at −172 °C: a = 9.883(3), b = 13.078(5), c = 8.323(2) Å; α = 97.02(2), β = 106.90(1), γ = 94.29(2)°; Z = 2; V = 1015 Å3. The structure was solved by direct methods (MULTAN) and refined to values of conventional indices R (Rw) of 4.72% (4.50%) using 2636 unique reflections with Fo > 3σ-(Fo). The two Rh2+ centers are bridged by three η1:η1µ2 AcO-groups over a Rh-Rh bond distanceof 2.475(2) Å. The coordination spheres of Rh(l) and Rh(2) are completed by chelating bpy and OAc- groups, respectively. The chelating OAc- is asymmetrically bound as a consequence of the axial/equatorial positioning of its two oxygen atoms O(27) and O(29). Compound 3 undergoes a reaction on dissolution in MeOH to give [Rh2(OAc)3(bpy)(MeOH)](OAc)·2MeOH (4) as determined by 1H NMR (1D- and 2D-homonuclear J-resolved spectroscopy), elemental analysis, conductivity measurements, and reactivity studies. Reaction of Rh2(O2CCF3)4(Me2CO)2 (2) with 1 equiv of bpy in CH2Cl2, followed by recrystallization of the product from THF/H2O, produces crystals of Rh2(O2CCF3)4(bpy)(THF)(H2O)-THF (5). Compound 5 crystallizes in the monoclinic space group Pc with the folowing cell parameters at −105 °C: a = 10.683(8), b = 9.170(8), c = 17.783(1) Å; α = 90.00, β = 103.52(7), γ = 90.00°; Z = 2, V = 1693 Å.3 The structure was solved by direct methods (MITHRIL) and refined to values of R (Rw) of 5.1% (5.8%) using 2493 unique reflections with F > 3σ(F). The two Rh2+ centers are bridged by two η1:η1:µ2 O2CCF3- ligands across a Rh-Rh separation of 2.520(3) Å. Coordination about Rh(l) is completed by two terminal η1-O2CCF3- groups in equatorial sites with the axial site being occupied by a water molecule. Rh(2) is ligated by a chelating bpy group in the equatorial plane, with axial ligation being provided by a THF molecule. Reaction mixtures comprising [Rh2(OAc)2(MeCN)6] (BF4)2 (6) and 1 equiv of bpy in MeCN lead to isolation of [Rh2(OAc)2(bpy)(MeCN)4](BF4)2·MeCN (7). Compound 7 crystallizes in the triclinic space group P1̄ with the following cell parameters at −170 °C: a = 12.381(2), b = 14.301(2), c = 12.246(2) Å; α = 94.60(1), β = 105.84(1), γ = 117.42(1)°; Z = 2; V = 1797 Å3. The structure was solved by direct methods (MULTAN) and refined to values of R (Rw) of 4.92% (5.74%) using 4723 unique reflections with F > 3σ(F). The two metals are bridged by two cis η1:η1:µ2-OAc- groups that span a Rh-Rh distance of 2.5395(8) Å. Coordination at Rh(l) is completed by a chelating bpy in the equatorial plane and an axial MeCN ligand, while the coordination sphere of Rh(2) is completed by two equatorial MeCN molecules and an axial MeCN molecule. © 1993, American Chemical Society. All rights reserved.

author list (cited authors)

  • Crawford, C. A., Matonic, J. H., Streib, W. E., Huffman, J. C., Dunbar, K. R., & Christou, G.

citation count

  • 34

publication date

  • July 1993