Rhodium nitro complexes as oxygen-transfer agents: oxidation of olefins

Is delocalization a driving force in chemistry? Benzene, allyl radical, cyclobutadiene, and their isoelectronic species

“…Once obtained, the A£dis values are compared with the total distortion energies, of ground-state allyl radical, in order to ascertain the role of -electronic delocalization more accurately than in Table II (6) C6H6 (septuple! ), 16" SCF + 14.5 + 13.7…”

“…For the sake of comparison, A£dis values are estimated also by the other two models used for allyl radical. In the first, -delocalization is "turned off" in the -septuplet state of benzene (16), and eq 5 is utilized to extract the A£dis value. In the second, A£dis is obtained by calculating the distortion energy of the bare -(C1+)6H6 framework (17).…”

“…A£dis(C6H6) is estimated also directly from the ground state (entries 1 and 4 in Table IV). These A£dis(C6H6) values may be considered to represent more faithfully the -frame than the A£dis(C6H6) values that are obtained from the high-spin state (16) and the bare -frame (17). At the STO-3G level, all three A£dis(C6H6) values are practically equal.…”

Nitrate‐ and Nitrite‐Assisted Conversion of an Acetonitrile Ligand Into an Amidato Bridge at an {Mo2(Cp)2(μ‐SMe)3} Core: Electrochemistry of the Amidato Complex [Mo2(Cp)2(μ‐SMe)3{μ‐η1,η1‐OC(Me)NH}]+

“…[14] In the case of transition-metal nitrite complexes, transfer of an oxygen atom to an organic substrate has also been observed, the NO 2 -ligand being N-bound (nitro coordination) to the metal. [15] In the present study, the similarity of the redox potentials of the intermediates . [16] Since the experiments were not conducted under rigorously anhydrous conditions, residual water in the solvent might be involved.…”

Catalytic oxidation of 1-hexene with molecular oxygen by iridium nitro complexes

“…A variety of nitro complexes of Pd [3][4][5][7][8][9][10]12], Rh [6], Co [2,9], Ru [13] and Fe [14,15] have been studied in the oxidation of olefms, however, no example of an iridium nitro complex has been studied. In this work we report the synthesis, IR characterization and the reactive properties of Ir(III) nitro complexes in the catalytic oxidation of 1-hexene to ketone and/or epoxide compounds by molecular oxygen in acetonitrile.…”