Model Ziegler-Type Hydrogenation Catalyst Precursors, [(1,5-COD)M(mu-O2C8H15)](2) (M = Ir and Rh): Synthesis, Characterization, and Demonstration of Catalytic Activity En Route to Identifying the True Industrial Hydrogenation Catalysts

Date

2009-02-02

Author

Alley, William M.
Girard, Chase W.
Özkar, Saim
Finke, Richard G.

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The compounds [(1,5-COD)M(mu-O2C8H15)](2) (COD = cyclooctadiene, M = Ir (1) or Rh (2), O2C8H15 = 2-ethylhexanoate) were synthesized by addition of Bu3NH(2-ethylhexanoate) or Na(2-ethylhexanoate) to acetone suspensions of [(1,5-COD)Ir(mu-Cl)](2) or [(1,5-COD)Rh(mu-Cl)](2), respectively. The synthesis of such well-defined second and third row model precursors is key to determining the true nature of commercial Ziegler-type hydrogenation catalysts (i.e., catalysts made from the combination of a non-zerovalent, group 8-10 transition metal precatalyst and a trialkylaluminurn cocatalyst), an unsolved, similar to 40 year old problem. The characterizations of 1 and 2 were accomplished by elemental analysis, melting point, FAB-MS, FT-IR, UV-vis, NMR spectroscopy, and single crystal X-ray diffraction. The complexes, C32H54Ir2O4 and C32H54O4Rh2, are isostructural: monoclinic, P2(1)/n, Z = 4. The lattice constants for 1 are a = 15.7748(5) angstrom, b = 9.8962(3) angstrom, c = 20.8847(7) angstrom, ss = 108.408(2)degrees. The lattice constants for 2 are a = 15.7608(4) angstrom, b = 9.9032(3) angstrom, c = 20.8:259(5) angstrom, ss = 108.527(1)degrees. Complexes 1 and 2 are dimeric, bridged by the 2-ethylhexanoates, and with one 1,5-COD ligand bound to each metal. The formally 16 electron metal atoms are in square ligand planes with dihedral angles between the planes of 56.5 degrees for 1 and 58.1 degrees for 2. The M-M distances of 3.2776(2) and 3.3390(4) angstrom for 1 and 2, respectively, fall in the range of similar structures thought to have some M-M interaction despite the lack of a formal M-M bond. Demonstration that active Ziegler-type hydrogenation catalysts are made when 1 or 2 combine with AlEt3 is provided, results that open the door to the use of 1 and 2 as well-defined third and second row congeners, respectively, of Ziegler-type hydrogenation catalysts. These compounds have proven important in addressing the previously unsolved problem of the true nature of the catalyst in industrial Ziegler-type hydrogenation catalyst systems; their high yield synthesis and unequivocal characterization reported herein are the necessary first steps of that work.

Subject Keywords

Physical and Theoretical Chemistry, Inorganic Chemistry

URI

https://hdl.handle.net/11511/62886

Journal

INORGANIC CHEMISTRY

DOI

https://doi.org/10.1021/ic801933b

Collections

Department of Chemistry, Article

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Citation Formats

W. M. Alley, C. W. Girard, S. Özkar, and R. G. Finke, “Model Ziegler-Type Hydrogenation Catalyst Precursors, [(1,5-COD)M(mu-O2C8H15)](2) (M = Ir and Rh): Synthesis, Characterization, and Demonstration of Catalytic Activity En Route to Identifying the True Industrial Hydrogenation Catalysts,” INORGANIC CHEMISTRY, pp. 1114–1121, 2009, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/62886.