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All geometries were optimized using the B3LYP functional and a mixed basis set of SDD for Ni and 631G(d) for other atoms. A larger base set, SDD for Ni and 6-311 + G(2d, p) for other atoms was used for single point energy calculations and solvation energy corrections using the CPCM model. Single point calculations using the B3P86 and B3PW91 functionals were also performed and give comparable results to the B3LYP calculations (see ESI† for details) The isopropyl groups on the SIPr ligand were replaced with methyls in the calculations to reduce computational cost. All calculations were performed using Gaussian 09. Gaussian 09, revision B.01, Gaussian, Inc., Wallingford CT, The Ni-catalyzed amination of aryl carbamates is not inhibited in the presence of galvinoxyl radical or BHT; thus, we propose that a Ni(i)/Ni(iii) catalytic cycle is likely not operative. For examples where additives such as galvinoxyl radical or BHT are used to probe the presence of Ni(i) intermediates, see
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-1) between complex 5 at the beginning and end of the plot represents the energy released in the catalytic cycle. ref. 31 Competition experiments between phenol-derived carbamates and sulfamates indicate that sulfamates are inherently more reactive than carbamates in both the nickel-catalyzed Suzuki-Miyaura coupling and amination. The preference for sulfamate coupling seen in the conversion of 18 → 20 is likely heightened because of the carbamate's ortho substituent
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