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Co(NO2) + X Co(NO) + XO
overall: 2 X + O2 2 XO
Background (2): Five-coordinate
(nitro)cobalt porphyrins vs. six-
coordinate
Much more reactive than the hexacoordinate
derivatives
Lewis acids remove trans ligand such as pyridine
Catalytically oxidize alkenes
May involve a peroxynitro intermediate
Oxidation competitive with comproportionation
Goodwin, et al. Inorg. Chem., 2001, 40, 4217-
4225.
Background (3): Proposed
oxygen activation/oxo-transfer
XO
Epoxides, aldehydes
X
non-radical
L4Co(III)NO2 L4Co(II)NO
C-H XO
insertion: O2
alcohols radical
L4Co(II)NO(O-O)
X
No comproportionation
Overall: 2X + O2 2 XO
Background (4): Other examples
of metal-bound peroxynitrite
intermediates
Hemes
(Hb and Mb - O-bound: FeO2 + NO (Nitric oxide dioxygenation)
Olson, Foley, et al. Free Rad. Biol. Med. 2004, 36, 685-697.
(N-bound: MbNO + O2)
Arnold, Bohle, 213th ACS Nat’l Meeting, San Francisco, 1997.
Other Iron
(N-bound: Fe(II)(CN)5NO + O2)
Videla, Olabe, et al. J. Am. Chem. Soc. 2007, 129, 278-279.
Copper
(CuO2 + NO)
Maiti, Karlin, et al. J. Am. Chem. Soc. 2008, 130, 6700-6701.
Background (5): Other examples
of metal-bound peroxynitrite
Cobalt
(O-bound: CoO2 + NO)
Wick, Kissner, Koppenol, Helv. Chim. Acta 2000, 83, 748–754.
N
+ CH3
N
+
N CH3 Schematic of a Nafion
monomeric unit
Pentacoordinate (nitro)cobalt
porphyrin, CoTMpyP(2), with The Nafion films are transparent
cationic pyridinium groups. and the reaction chemistry on
these films parallels the solution
chemistry – so visible spectra can
be used to identify derivatives on
films.
Preparation of [CoTMpyP(NO2)]4+
on Nafion
H2O H2O CH3CH2OH
N N +NO2- N N +EtOH N N
CoIII CoIII CoIII
N N N N N N
-
Br H 2O
Br NO2 NO2
H2 O H2 O EtOH
N N N N
Co II + NO2 ?? III
Co
N N N N
NO2
Reaction Chemistry
H2O CH3CH2OH
N N N N +EtOH N N
III
Co Co III
Co III
N N N N N N
H2O
NO2 NO2 NO2
+ Ph3P
+ Ph3PO + H2O
EtOH + Ph3PO
N N
II
Co
N N
O
NO
O OH
N N
Proposed coupled N
CoIII
N
triphenylphosphine N
CoII
N O2 + L N
CoIII
N
N N N N
and cyclohexene NO N
O O
O
O
+ +
Goodwin, et al. Inorg. O OH
+ +
NO2
O OH
Computational Chemistry - 1
C oPO + N O + 1 / 2 O 2
Calculated values C oP + N O 2 + 1 / 2 O 2
of standard free
energy changes (at
298 K, determined 203.58 kJ/m ol
by DFT-BP-6-31G* 191.9 kJ/m ol
methods) for
conversion of five- C oP N O O 2
coordinate
[CoTMpyP(NO2)]4+
to some possible
111.11 kJ/m ol
intermediates in the
oxygen activation
catalysis. C oPN O + O 2
14.92 kJ/m ol C oPN O 2 + 1 / 2 O 2
C oP O N O + 1 / 2 O 2
-9.24 kJ/m ol
Computational Chemistry - 2 Co(II)P + NO + O2
by [CoTMpyP(NO2)]4+ CoP(O2) + NO
-43.5 kJ/mol
drawn approximately
CoPOONO (singlet)
to scale. -3.4 kJ/mol
CoPOONO (triplet)
203.6 kJ/mol
111.1 kJ/mol
CoPNO + O2
14.9 kJ/mol CoPNO2 + 1/2 O2
CoPONO + 1/2 O2
-9.2 kJ/mol
Computational Chemistry - 3 CoPNO2O + H2O
-126.0 kJ/mol
(H2O)CoPNO2 + 1/2 O2
Acknowledgements
NFSAT-CRDFARC2 -3231-YE-04
NSF OISO/IRES-0622810
CCU students: Jennifer Coor; Don Kavanagh;
Mathieu Sabbagh; James Howard; John
Adamec; Deidre Parmley; Emily Tarsis; Astghik
Hovhannisyan
Tigran Kurtikyan (Molecular Structure Research
Center, Yerevan, Armenia)
Patrick Desrochers (U Central Arkansas, epr)