[3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes

Table 1

Activation barriers for the formation of the dinitrosoalkanes through and addition involving various olefins. All energies are measured in kcal mol⁻¹.

Olefin/substituent	Cobalt			Rhodium			Iridium
	Ethylene	+11.2	+39.8	+28.9	+14.2	+42.6	+34.3	+13.0	+39.4	+37.8
Propene	+11.8	+44.5	+29.6	+14.7	+43.2	+36.0	+13.4	+43.7	+39.3
Transbutene	+10.9	+41.1	+29.1	+14.3	+43.5	+36.2	+13.0	+39.6	+39.1
2,3-Dimethyl-2-butene	+10.4	+40.6	+34.8	+12.6	+43.0	+40.8	+12.4	+38.2	44.9
Ethenol	+10.1	+44.6	+34.3	+13.3	+47.6	+38.8	+11.5	+43.3	+44.3
Aminoethene	+10.1	+49.0	+30.5	+12.9	+49.9	+35.7	+11.5	+47.8	+39.8
Vinyl fluoride	+13.0	+47.5	+35.7	+16.5	+53.2	+40.4	+15.0	+46.2	+45.7
Acrylonitrile	+11.0	+38.7	+31.8	+15.2	+42.5	+36.5	+13.3	+42.8	+41.8
3,3,3-Trifluoro-1-propene	+12.1	+42.1	+31.7	+16.0	+43.7	+36.6	+14.7	+41.9	+40.8
Cyclobutene	+10.9	+41.4	+30.1	+13.4	+43.1	+35.7	+12.9	+39.7	+38.8
Cyclopentene	+13.7	+38.6	+33.7	+16.7	+43.3	+40.3	+15.6	+38.9	+43.9
2-Cyclohexenone	+10.6	+34.8	+33.1	+17.0	+40.8	+42.6	+15.7	+36.6	+46.4
2-Norbonene	+9.0	+33.8	+44.8	+11.3	+36.3	+49.9	—	+31.5	+52.9

of the first step of the two-step pathway. of the second step of the two-step pathway.