Catalytic oxidations using ruthenium porphyrins - Advances in Catalytic Activation of Dioxygen by Metal Complexes - page 60

1-octene in at 40°C for 2 h (Ru : substrate : PhINTs = 1 : 75 : 150)
generated the aziridines with conversions of 32, 43 and 42%, respectively 214 .
The amidation reactions under such conditions (for example, with indane,
adamantane and 1,2-dihydronaphthalene) resulted in corresponding amides
in high conversions (92-99%) of substrate. Use of a lower temperature, or
use of benzene or MeCN, gave poorer results 214 . Of interest, use a mixture of
and (R = Ts, Ns, instead of PhINR itself, for
aziridination and amidation of alkenes and alkanes with Mn(TPFPP)Cl as a
catalyst, gave excellent substrate conversions, but the corresponding Ru
system was not tested 214 .
Enantioselective amidation of saturated C-H bonds has also been
reported by Che's group 213 . Application of or a mixture
of as a catalyst 40°C, Ru :
PhINTs : substrate = 1 : 100 : 500) for a range of substrates such as
ethylbenzene afforded corresponding amides in yields of 16 to 47% and ee
values of 6-48%, all with excess S -configuration 213 .
Attempts to synthesis bis(imido) compounds via oxidative bromination of
led to formation of the oxo(imido) species
(eq. 46, porp = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP,
3,5-Cl-TPP), that were isolated and characterized 68,196,200 , where the source
of the oxo-ligand was most likely trace amount of water present in the
solvent 68,196 . The oxo(imido) complexes were more stable than the
corresponding dioxo species, being air-stable in the solid state, but gradually
decomposing in to form the nitrosyl complexes Ru(porp)(NO)(OH).
The species react with amines or phosphines to yield
the respective bis(amine)- and complexes 200 , but

the fates of the oxo and imido ligands were not determined. The
corresponding

and species do not react

with and reactivity with is very slow.

The nitrido complex is said to be formed via

reaction of with aq. in although an attempt

to make the nitride complex via oxidation of with m-

or air was not successful 220 . In contrast, oxidation of
complexes (porp = TPP, TTP, 4-C1-TPP) with m -CPBA in a
mixture

CPBA,

under reflux gave the corresponding

species 200 .