An N-Bound Peroxynitro-Cobalt

Intermediate? Computational and

Experimental Evidence

John A. Goodwin, Donald F. Kavanagh,

Tigran S. Kurtikyan, Jean Standard,
Patrick Desrochers
Coastal Carolina University, Conway, SC
Molecular Structure Research Centre NAS, Yerevan, Armenia
Illinois State University, Normal IL
University of Central Arkansas, Conway, AR
Background (1): Oxygen Activation/
Secondary Oxo Transfer Catalysis
 (py)CoTPP(NO2)/(with Lewis acids) – since late
’70’s (Tovrog, Diamond, Mares J. Am. Chem. Soc.
1979, 101, (1), 270-272)
 Nitro/nitrosyl complexes and Oxygen Activation with
N-bound peroxynitro intermediate (Clarkson, Basolo
Inorg. Chem. 1973, 12, (7), 1528-1534)
 Co(NO) + O2  Co{(N=O)(O2)}

 Co{(N=O)(O2)} + Co(NO)  2 Co(NO2)

(comproportionation mechanism) and/or
 Co{(N=O)(O2)} + X  Co(NO2) +XO

 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.

Thyagarajan, Incarvito, Rheingold, Theopold, Inorg. Chim. Acta

2003, 345, 333–339. Not observed.
 Project Goals and Objectives
 Adapt solution-phase catalysis as a
heterogeneous catalysts
 Use cationic porphyrins electrostatically immobilized on
Nafion films
 Use gas-phase reactants
 Probe catalytic mechanism
 immobilized nitro complex to avoid comproportionation
 Computational study to compare plausible
intermediates
 Goodwin, J.A. et al. Inorg. Chem. 2008, 47, (17),
7852-7862.
 Structures
H3C
+
+ N
N
H3C
N
NO 2
N Co N

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

BH4- Heat and Vacuum

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

Both processes are catalytic in the presence of O2

 Proposed Catalytic Pathway
L

N N

Proposed coupled N
CoIII
N

pathways of L = EtOH or H2O

NO2 Ph3PO

Six coordinate Ph3P

(nitro) complexes Ph3P

EtOH + Ph3PO
with L

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

Chem. 2008, 47(17) 7852-7862

N N
CoIII
N N O

+ +
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

Plotted values of 40.9 kJ/mol 38.4 kJ/mol

standard free energy Co(II)P + NO2 + 1/2 O2 CoPO + 1/2 O2 + NO

changes (at 298 K,

determined by DFT -133.8 kJ/mol

BP 6-31G* methods) 191.9 kJ/mol

82.7 kJ/mol
for possible catalytic
dioxygen activation CoPNO2O

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

Calculated values of 44.5 lK/mol

standard free energy (H2O)CoPNO2O

changes (at 298 K, -126.0 kJ/mol

determined by DFT- 111.1 kJ/mol

102.0 kJ/mol
BP-6-31G* methods)
for possible catalytic
dioxygen activation CoPNO2 CoPNO + O2 + H2O
1
by [CoTMpyP(NO2)]4+ + /2 O2 + H2O
+14.9 kJ/mol
-35.6 kJ/mol
and its aqua -82.4 kJ/mol (H2O)CoPNO + O2

complexes. +61.7 kJ/mol

-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)