Electrochemistry of molybdenum imides: cleavage of molybdenum–nitrogen triple bonds to release ammonia or amines †

Energetics and Mechanism of Ammonia Synthesis through the Chatt Cycle: Conditions for a Catalytic Mode and Comparison with the Schrock Cycle

“…These reactions have been observed for diazenido, hydrazido and imido intermediates. [8,31] Nevertheless, this dissociation is induced by a twoelectron reduction, which can be achieved electrochemically or by dehalogenation with tBuLi, whereas in our reaction cycle only one-electron reduction steps occur. Furthermore it could be shown for the imido intermediates that five-coordinated compounds were only formed under aprotic conditions.…”

“…Furthermore it could be shown for the imido intermediates that five-coordinated compounds were only formed under aprotic conditions. [31] In our cycle, in contrast, every one-electron reduction is followed by protonation. The coordination of better leaving groups like TsO À would certainly favor five-coordinated species, but for fluoride as trans ligand it appears that this possibility can be excluded under the applied conditions.…”

“…Importantly, the described reaction sequence is entirely analogous to the mechanism that has been derived for the protonation and reduction of Mo IV alkylimido complexes from electrochemical investigations in the presence of acids. [31] In this study a combined protonation/reduction step from the Mo II -(alkyl)amido complex to the Mo I amine complex is postulated. From our calculations, we conclude that the Mo II -amido complex 7 c is first protonated to a Mo II -ammine complex (8 a) which is then reduced to the Mo I -ammine complex 8 b.…”

Chloridobis[1,2-bis(diphenylphosphino)ethane](ethylimido)molybdenum(IV) tetraphenylborate acetonitrile disolvate

“…For related literature, see: Alias et al (1997); Bruno et al (2002); Chatt & Dilworth (1977); George & Noble (1978); Mersmann et al (2006).…”

Organic–inorganic hybrid matrix doped with alkenyldiazenido complexes of molybdenum

“…and mesoporous materials such as zeolites, clays and mesoporous structures have been used as hosts for the encapsulation or noncovalent attachment of metal complexes [8][9][10][11][12][13]. The combination of the sol-gel method with the host-guest concept has successfully led to production of a significant multifunctional organic-inorganic framework with tunable design and appropriate characteristics for heterogeneous catalysis [7,14,15]. These systems combine many advantages of homogeneous (high activity, high selectivity and high reproducibility) and heterogeneous (easy separation and recovery of the catalysts from the reaction mixture) catalysis.…”