Anda di halaman 1dari 20

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
 Adaptsolution-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
NO2
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)CoTMpyP(2)Br]Br4 is prepared by synthesis of
tetra(pyridyl(2))porphyrin, followed by methylation and
metal insertion.
 Irreversible adsorption onto sodium-form films from
aqueous solution gives [(H2O)CoTMpyP(2)Br]/Naf
 Treatment with sodium nitrite solution gives
[(H2O)CoTMpyP(NO2)]/Naf (Soret shift from 430 nm to 428
nm)
 Treatment with absolute ethanol gives
[(EtOH)CoTMpyP(NO2 )]/Naf (Soret shift from 428 to 425
nm)
 UV-vis spectra parallel changes observed in solution that
were verified by FTIR. FTIR not feasible in the Nafion
system.
Preparation of [CoTMpyP(NO2)]4+
on Nafion
 Reduction of [(H2O)CoTMpyP(2)Br]/Naf with
Bu4NBH4 in DCM under nitrogen atmosphere
(glove box) gives air-sensitive
[(H2O)CoTMpyP(2)]/Naf. (Soret shift from 430
nm to 408 nm with EPR signal of five coordinate
cobalt(II))
 Heating [(EtOH)CoTMpyP(NO2 )]/Naf gives
pentacoordinate [CoTMpyP(NO2 )]/Naf (Soret
shift from 428 nm to 419 nm)
Preparation of [CoTMpyP(NO2)]4+
on Nafion
H2O H2O CH3CH2OH

N N +NO2- N N +EtOH N N
III
Co Co III
Co III
N N N N N N
Br- H2O
Br NO2 NO2

BH4- Heat and Vacuum

H2 O H 2O EtOH

N N N N
CoII + NO2 ?? III
Co
N N N N

NO2
Reaction Chemistry
 Treatmentof [(EtOH)CoTMpyP(NO2 )]/Naf with
Ph3P in DCM or Ethanol under N2 gives
[CoTMpyP(NO)]/Naf
 Ph3P is a very strong O-atom acceptor, Soret shift to
417 nm
 Ph3P can form six-coordinate nitro complex, but Soret
at 432 nm)
 Treatment of [(EtOH)CoTMpyP(NO2 )]/Naf with
Ph3P in ethanol under O2 gives catalytic
formation of Ph3PO (1 cm x 2 cm film, 3 mL of
1mM Ph3P, 12 hours)
 Catalysis is sustained by isolated porphyrin, turnover
of 66 with turnover frequency of 5.5 hr-1 at room temp
Reaction Chemistry
 Treatmentof [CoTMpyP(NO2 )]/Naf with gas
phase cyclohexene under N2 gives
[CoTMpyP(NO)]/Naf (85°C)
 Five-coordinate nitro complex retains O-atom transfer
strength
 Treatment of [CoTMpyP(NO2 )]/Naf with
cyclohexene and O2
 catalytic formation of cyclohexene oxide (7-oxa-
bicycloheptane), 2-cyclohexene-1-one, and 2-
cyclohexene-1-ol (85°C) (product analysis by GC-
MS)
 Catalysis is sustained by isolated porphyrin with gas-
phase O-atom acceptor
 Quantitative measurements not available yet
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
CoPO + NO + 1/2 O2

 Calculated values CoP + NO2 + 1/2 O2

of standard free
energy changes (at
298 K, determined 203.58 kJ/mol
by DFT-BP-6-31G* 191.9 kJ/mol

methods) for
conversion of five- CoPNOO2

coordinate
[CoTMpyP(NO2)]4+
to some possible 111.11 kJ/mol
intermediates in the
oxygen activation
catalysis. CoPNO + O2
14.92 kJ/mol CoPNO2 + 1/2 O2
CoPONO + 1/2 O2
-9.24 kJ/mol
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 O 2 + H2 O
+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
An N-bound peroxynitro
intermediate?
XO O2

CoP(NO)
Proposed solution X
phase oxygen
activation/oxo- O
CoP(NO2) PCo N
transfer cycle
O O
(without
comproportionation
step)
XO X
overall:
2 X + O2 2 XO
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)