Electrophilic aryl C–H amination by dimetal nitrides: correlating electronic structure with reactivity

Metal–metal multiple bonded intermediates in catalysis

“…19 Further computational study has explored the energetics of the electrophilic aromatic substitution mechanism using a series of hypothetical M-Ru≡N and M-Mo≡Nc o mpounds as well as mononuclear Ru≡Na n dM o ≡N models, in order to determine the role of the metalmetal bond in C-H amination reactivity. 34 Through analysis of all the energetics of these reactions, two generalizations were made. First, transition state energies were uniformly higher in energy for mononuclear M≡N compounds than they were for binuclear metalmetal bonded M 2 nitrido compounds, signifying that the M-M≡N electronic structure greatly facilitates C-H amination via the electrophilic aromatic substitution Scheme 7.…”

“…Secondly, transition state energies were uniformly higher for M-Mo≡N compounds than they were for M-Ru≡N compounds, consistent with greater electrophilicity of the latter species. 34 In order to disfavour intramolecular reactions, a new Ru 2 -nitride precursor was designed that utilizes the Ru 2 (chp) 4 core (chp = 6-chlorohydroxypyridinate). The compound Ru 2 (chp) 4 Cl was reported in 1985 by Chakravarty et al 35 and its structure was found to have a '4.0' configuration in which all the O atoms bind to one Ru atom and all the N atoms bind to the other Ru atom as indicated in scheme 7.…”

Tuning catalytic activity of dimolybdenum paddlewheel complexes by ligands: mechanism study on the radical addition reaction of CCl4 to 1-hexene

“…Since the rst dimolybdenum complex (molybdenum(II) acetate) containing Mo-Mo multiple bond was isolated and characterized [1], a large number of polymetal-metal bonding complexes have been synthesized [2][3][4][5][6][7][8]. In particular, the metal-metal bonded compounds with unique paddlewheel structures have played a major role in development of coordination chemistry [9] and continue to be of interest for their catalytic [10], photophysical [11], electronic [12], and structural properties [13] as well as reactivity [14,15]. Among these paddlewheel compounds, dimolybdenum compounds (denotes as Mo 2 L 4 ) have attracted much more attention due to their unique con guration and catalytic applications [16][17][18][19][20][21].…”

Synthesis, characterization and solution behavior of a systematic series of pentapyridyl-supported RuII complexes: comparison to bimetallic analogs

“…49–54 A topic of special interest is the role of the metal–metal bond in these complexes, which can be best elucidated by direct comparisons with monometallic analogues (Scheme 1). 53,55…”