Reactions af Dioxo[N-( salicylidene)-2-aminophenolato-N,O,O' ](hexamethyl-phosphoramid)molybdenum(VI) Complexes with Substituted Hydrazines and Chemistry af Molybdenum(VI)-Hydrazido Complexes

Mikael Retbøll, Eval Rud Møller, Rita G. Hazell, Karl Anker Jørgensen

Publikation: Bidrag til tidsskriftTidsskriftsartikelForskningpeer review


The reaction of dioxo[N-(salicylidene)-2-aminophenolato-N,0,0’ ](hexameth-
ylph0sphoramide)molybdenum(Vl), 4a, and its C-imine substituted derivatives,
4b,c with different mono- and di-substituted hydrazines has been investigated. The
reaction of 4a with 1,1-dimethylhydrazine leads to decomposition of the complex.
When complex 4b is treated with 1,1-dimethylhydrazine an 111-coordinated hy-
drazido(2-) molybdenum complex, 8a, is formed. The 2-aminophenolato-N,0
ligand present in 8a originates from cleavage of the salicylidene ligand in 4b. The
structure of 8a is determined by an X-ray crystallographic investigation. The elec-
tronic structure of 4b and 8a is investigated using extended Htickel calculations
and based on the results for 4a, a mechanism for the formation of 8a is postulated.
The chemical properties of 8a are discussed on the basis of its electronic structure.
A general method for the preparation of a series of complexes similar to 8a has
been developed. A minor product is also formed in the reaction of methylhydra-
zine with 4b and the possible structures of this complex are discussed; it is pos-
tulated that the hydrazido ligand in this complex might coordinate to the mo-
lybdenum atom in an 112-fashion. The chemical properties of the nl-coordinated
hydrazido(2 —) molybdenum complex, 8a, have been investigated and reactions
with e.g. hydrogen chloride, dimethyl sulfate, benzaldehyde and benzoyl chloride
have been performed.
TidsskriftActa Chemica Scandinavica
Sider (fra-til)278-290
Antal sider13
StatusUdgivet - 1995
Udgivet eksterntJa