Bexrud, Jason A. Li, Chunyu Schafer, Laurel L. Enhanced Reactivity Results in Reduced Catalytic Performance:  Unexpected Ligand Reactivity of a Bis(<i>N</i>-2,6-diisopropylphenylperflourophenyl-amidate)titanium-bis(diethylamido) Hydroamination Precatalyst A bis(amidate)titanium-bis(amido) complex incorporating electron withdrawing pentafluorophenyl substituents has been prepared to enhance reactivity in this class of hydroamination precatalyst. This bis(<i>N</i>-2,6-diisopropylphenylperflourophenylamidate)titanium-bis(diethylamido) titanium complex has been fully characterized, including its X-ray crystal structure. As a precatalyst, the title compound proved to be effective for intermolecular hydroamination of internal and terminal alkynes with primary amines with yields as high as 97% and modest intramolecular alkene hydroamination. However, the elevated reactivity of this complex also resulted in reduced Markovnikov/anti-Markovnikov selectivity with some terminal alkynes. Substrate scope limitations revealed that this complex is susceptible to decomposition as a direct consequence of nucleophilic addition of the amine substrate to the pentafluorophenyl substituent of the amidate ligand. intramolecular alkene hydroamination;terminal alkynes;pentafluorophenyl;reactivity;precatalyst;Enhanced Reactivity Results;Substrate scope limitations;X-ray crystal structure;bi;substituent 2020-04-02
    https://acs.figshare.com/articles/journal_contribution/Enhanced_Reactivity_Results_in_Reduced_Catalytic_Performance_Unexpected_Ligand_Reactivity_of_a_Bis_i_N_i_-2_6-diisopropylphenylperflourophenyl-amidate_titanium-bis_diethylamido_Hydroamination_Precatalyst/12066870
10.1021/om700653t.s001