1246956-75-1Relevant academic research and scientific papers
Reactivity and regioselectivity of insertion of unsaturated molecules into M-C (M = Ir, Rh) bonds of cyclometalated complexes
Li, Ling,Jiao, Yunzhe,Brennessel, William W.,Jones, William D.
, p. 4593 - 4605 (2010/12/20)
The reactivity of four different cyclometalated iridium and rhodium complexes (1, Ir-N-Me; 2, Rh-N-Me; 3, Ir-N-Py; 4, Rh-N-Py) with ancillary ligands with different electronic and steric properties has been investigated by reactions of ethylene (a), propylene (b), carbon monoxide (c), tert-butylisocyanide (d), acetylene (e), and phenylacetylene (f). Only coordination products were obtained for the reactions of ethylene and propylene with 1 and 3, while inserted and rearranged products were achieved for the reactions with 2 and 4. Insertion of a single equivalent of acetylene was observed for the reactions with 2, 3, and 4, whereas reaction with 1 produces a product in which 4 equiv of acetylene has undergone insertion. The reactions with carbon monoxide showed clean M-C bond insertion products, while tert-butylisocyanide formed only terminal adducts. Two equivalents of phenylacetylene were observed to insert for all of the cyclometalated complexes. The regioselectivity was also investigated for each cyclometalated complex by using a series of internal unsymmetrical alkynes, and the results revealed that the regioselectivity was controlled by both steric and electronic factors. The insertion compounds were fully characterized by 1H NMR spectroscopy, 13C NMR spectroscopy, elemental analysis, and X-ray determinations for selected cases.
