Related Experiment Video
Updated: Oct 13, 2025
Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Heterobimetallic complexes stabilized by the P2N2 macrocyclic ligand system: synthesis and reactivity of a
Siyuan L Xie1, Corey A Sanz1, Michael D Fryzuk1
1Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada, V6 T 1Z1. fryzuk@chem.ubc.ca.
Abstract:
The synthesis and reactivity of the bimetallic rhodium-copper complex, Rh(COE)[P2N2]Cu, which is stabilized by the P2N2 macrocycle, is reported. In the solid state, the rhodium and copper centers are on opposite sides of the macrocyclic ring with the Cu(I) in a linear environment and the Rh(I) in a square planar array. However, in solution a very symmetrical structure is suggested on the basis of the 1H NMR data, which is consistent with at least two separate fluxional processes, rotation of the cyclooctene unit and movement of the Rh(I) unit between the two amido donors. Addition of H2 to Rh(COE)[P2N2]Cu results in the formation of ([P2N2H]RhH(μ-H)2Cu)2via hydrogenation of the coordinated cyclooctene unit, oxidative addition of H2 to the rhodium center and hydrogenolysis of the copper amido unit. Monitoring the reaction of H2 by NMR spectroscopy indicated the formation of a number of intermediates which suggests hydrogenolysis of the copper amido linkage occurs to generate CuH in some form, along with Rh(COE)[P2N2H], which is converted to Rh(H)2[P2N2H] by hydrogenation of the cyclooctene, which then recombines with the CuH present to generate the final product. Deuteration studies indicate that there is considerable H/D scrambling in the cyclooctane produced that we attribute to reversible beta-elimination, migratory insertion steps.
More Related Videos
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Related Concept Videos
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
02:13Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...