Ultrafast spectroscopic and matrix isolation studies of p-biphenylyl, o-biphenylyl, and 1-naphthylnitrenium cations

Article abstract of DOI:10.1021/ja071325j

p-Biphenylyl, o-biphenylyl, and 1-naphthyl azides were deposited in argon at low temperature in the presence and absence of HCl. In the absence of HCl, the known electronic and vibrational spectra of the corresponding triplet nitrenes, azirines, and dideh

Full text of DOI:10.1021/ja071325j

Published on Web 06/13/2007
Ultrafast Spectroscopic and Matrix Isolation Studies of
p-Biphenylyl, o-Biphenylyl, and 1-Naphthylnitrenium Cations
Jin Wang,† Gotard Burdzinski,‡ Zhendong Zhu,† Matthew S. Platz,*,†
Claudio Carra,§ and Thomas Bally*,§
Contribution from the Department of Chemistry, The Ohio State UniVersity, 100 West 18th
AVenue, Columbus, Ohio, 43210, Quantum Electronics Laboratory, Faculty of Physics, Adam
Mickiewicz UniVersity, 85 Umultowska, Poznan 61-614, Poland, and De´partement de Chimie,
UniVersite´ de Fribourg, Chemin du Muse´e 9, CH-1700 Fribourg, Switzerland
Received February 25, 2007; E-mail: platz.1@osu.edu; Thomas.Bally@unifr.ch
Abstract: p-Biphenylyl, o-biphenylyl, and 1-naphthyl azides were deposited in argon at low temperature in
the presence and absence of HCl. In the absence of HCl, the known electronic and vibrational spectra of
the corresponding triplet nitrenes, azirines, and didehydroazepines were observed, whereas in the presence
of HCl, photolysis of these azides produces new electronic spectra assigned to the corresponding nitrenium
cations. For p-biphenylyl azide the resulting spectrum of the nitrenium ion is very similar to the previously
observed solution-phase spectrum of this species. The vibrational spectrum of this cation was recorded
for the first time. Spectroscopic evidence for the previously unknown o-biphenylylnitrenium cation and
1-naphthylnitrenium cation are provided. The spectra of p- and o-biphenylylnitrenium cations and
1-naphthylnitrenium cation are well reproduced by CASSCF and CASPT2 calculations. The same nitrenium
cations were detected in solution by femtosecond time-resolved laser flash photolysis of the appropriate
azides in 88% formic acid. The transient spectra of the nitrenium cations recorded in solution are in good
agreement with the spectra obtained in HCl matrices. The rates of formation of these cations equal the
rates of decay of the singlet nitrenes in 88% formic acid and are as follows: p-biphenylyl (τgrowth ) 11.5
ps), o-biphenylyl (τgrowth ) 7.7 ps), and 1-naphthylnitrenium cations (τgrowth ) 8.4 ps). The decay lifetimes
of p- and o-biphenylylnitrenium cations are 50 and 27 ns, respectively. The decay lifetimes of 1-naphthyl-
nitrenium cation is 860 ps in 88% formic acid.
1. Introduction
The understanding of arylnitrenes developed more rapidly
than that of nitrenium cations, mainly due to a lack of convenient
precursors for the latter. Aryl azides are readily available, and
the photolysis of parent phenyl azide leads to the production of
singlet nitrene 11, benzazirine 2, didehydroazepine 3, and triplet
Arylnitrenium cations and their conjugate bases, arylnitrenes,
are reactive intermediates of fundamental importance.1-5 Arylni-
trenium cations form covalent adducts with the guanine residues
of DNA by a typical electrophilic aromatic substitution pro-
cess.6,7 The formation of these adducts can be correlated with
the carcinogenic activity of aryl amines.8,9
Arylnitrenes, which have a quite unique electronic structure,
are important intermediates in synthetic organic chemistry and
in the attachment of small, highly functionalized molecules to
biomolecules and synthetic polymers.10-12
3
nitrene 1 (Scheme 1). These types of reactive intermediates
have been characterized by several physical techniques including
flash photolysis in solution phase with UV-vis and IR detection
and matrix isolation EPR, IR, UV-vis, and emission
spectroscopy.10-12
In recent years, the groups of Falvey,13-16 McClelland,1-4
and Novak17-22 have developed convenient precursors for
† The Ohio State University.
(10) Gritsan, N. P.; Platz, M. S. Chem. ReV. 2006, 106, 3844-3867.
(11) Pritchina, E. A.; Gritsan, N. P.; Bally, T. Phys. Chem. Chem. Phys. 2006,
8, 719-727.
‡ Adam Mickiewicz University.
§ Universite´ de Fribourg.
(1) Davidse, P. A.; Kahley, M. J.; McClelland, R. A.; Novak, M. J. Am. Chem.
Soc. 1994, 116, 4513-4514.
(12) Carra, C.; Nussbaum, R.; Bally, T. Chem. Phys. Chem. 2006, 7, 1268-
1275.
(2) McClelland, R. A.; Davidse, P. A.; Hadzialic, G. J. Am. Chem. Soc. 1995,
117, 4173-4174.
(13) Anderson, G. B.; Falvey, D. E. J. Am. Chem. Soc. 1993, 115, 9870-9871.
(14) Robbins, R. J.; Yang, L. L. N.; Anderson, G. B.; Falvey, D. E. J. Am.
Chem. Soc. 1995, 117, 6544-6552.
(3) McClelland, R. A. Tetrahedron 1996, 52, 6823-6858.
(4) McClelland, R. A.; Kahley, M. J.; Davidse, P. A.; Hadzialic, G. J. Am.
Chem. Soc. 1996, 118, 4794-4803.
(15) Srivastava, S.; Falvey, D. E. J. Am. Chem. Soc. 1995, 117, 10186-10193.
(16) Kung, A. C.; Falvey, D. E. J. Org. Chem. 2005, 70, 3127-3132.
(17) Novak, M.; Kahley, M. J.; Eiger, E.; Helmick, J. S.; Peters, H. E. J. Am.
Chem. Soc. 1993, 115, 9453-9460.
(5) Falvey, D. E. In ReactiVe Intermediate Chemistry; Moss, R. A., Platz, M.
S., Jones, M., Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, 2004; pp
593-650.
(18) Novak, M.; Kahley, M. J.; Lin, J.; Kennedy, S. A.; Swanegan, L. A. J.
Am. Chem. Soc. 1994, 116, 11626-11627.
(6) McClelland, R. A.; Ahmad, A.; Dicks, A. P.; Licence, V. E. J. Am. Chem.
Soc. 1999, 121, 3303-3310.
(19) Novak, M.; Kennedy, S. A. J. Am. Chem. Soc. 1995, 117, 574-575.
(20) Novak, M.; Kazerani, S. J. Am. Chem. Soc. 2000, 122, 3606-3616.
(21) Novak, M.; Rajagopal, S. AdV. Phys. Org. Chem. 2001, 36, 167-254.
(22) Novak, M.; Rajagopal, S. Chem. Res. Toxicol. 2002, 15, 1495-1503.
(7) Cheng, B.; McClelland, R. A. Can. J. Chem. 2001, 79, 1881-1886.
(8) Miller, J. A. Cancer Res. 1970, 30, 559-576.
(9) Miller, E. C. Cancer Res. 1978, 38, 1479-1496.
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J. AM. CHEM. SOC. 2007, 129, 8380-8388
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Ultrafast Spectroscopy of Arylnitrenium Cations
A R T I C L E S
transient spectrum of the phenylnitrenium cation.4,27 From
competition studies its lifetime was estimated to be ∼30 ps,
which is too short to allow its observation by nanosecond
spectroscopy. Thus, ultrafast time-resolved techniques are
necessary to directly observe certain nitrenium ions in solution.
Scheme 1
The intrinsic drawback of McClelland’s method is that the
protonation of the singlet nitrene has to be rapid enough to
compete with its other deactivation channels, such as intersystem
crossing to the lower energy triplet state and intramolecular
rearrangement (see Scheme 1).
o-Biphenylylnitrene 8 and 1-naphthylnitrene 15 are well-
known short-lived singlet nitrenes, whose lifetimes in CH3CN
(16 and 12 ps, respectively)28,29 are controlled by intramolecular
cyclizations (Schemes 3 and 4). Thus, even if protonation can
compete with the other decay channels, ultrafast spectroscopic
methods would be required to resolve the formation of these
nitrenium cations.
studying the solution-phase chemistry of nitrenium cations,
which allowed the measurement of their lifetimes, the deter-
mination of their UV-vis and IR spectra, and the determination
of rate constants for reactions with selected nucleophiles, in
aqueous solution. In the early 1990s, Falvey’s group reported
the first laser flash photolysis (LFP) study on nitrenium
cations, which they obtained by photoisomerization of anthra-
nilium cations,13 i.e., precursors that inherently carry a
carbonyl group on the aromatic ring. Later, they developed more
general photochemical precursors such as N-aminopyridinium
cations.13-15,23,24
In principle, any nitrenium cation can be generated from such
precursors, but monosubstituted N-aminopyridinium cations
(pyr+-NHR) are unstable. The most convenient way to generate
monosubstituted nitrenium cations, RNH+, was developed by
McClelland et al. who photolyzed aryl azides in water to
generate singlet nitrenes, which are subsequently protonated to
form nitrenium cations.1-4 This method works particularly well
when the singlet nitrene to be intercepted has a relatively long
lifetime (>10 ns) in aprotic solvent at ambient temperatures.
In this manner, p-biphenylylnitrenium cation 6, produced by
protonation of nitrene 5, was readily detected by transient UV-
vis spectroscopy (Scheme 2).1-4 Zhu et al. subsequently studied
this nitrenium cation in water using time-resolved resonance
Raman spectroscopy and assigned the spectra with the aid of
DFT calculations.25
A number of nitrenium cations have been characterized by
transient absorption spectroscopy experiments, and a good deal
has been learned about their lifetimes and rate constants for
reactions with other species. However, there are few direct
experimental measurements of the structure of these short-lived
species. Time-resolved infrared absorption spectroscopy (TRIR)
experiments have recently been used to obtain vibrational spectra
of several nitrenium cations, generated by flash photolysis of
aminopyridinium salts. The first such study confirmed that the
diphenylnitrenium cation has an iminocyclohexadienyl cation-
like structure.24
The lifetimes of singlet arylnitrenes are temperature depend-
ent. At low temperatures the thermally activated intramolecular
rearrangements become slow, and singlet nitrene lifetimes
increase to ∼100 ns and are limited by intersystem crossing to
the lower energy triplet state (cf., Schemes 1-4). This led us
to hypothesize that photolysis of aryl azides in argon/HCl
matrices might lead to efficient capture of singlet nitrenes and
produce nitrenium cations that are persistent under the conditions
of matrix isolation, which would allow their convenient
spectroscopic analysis. Also, matrix conditions lead to higher
resolution spectra of molecules than those that can be obtained
in solution, particularly in the case of vibrational spectroscopy.30
In this study, we will apply ultrafast UV-vis spectroscopy
to study reaction rates and mechanisms, complemented by
matrix isolation spectroscopy, to collect structural informa-
tion. As a first substrate in these experiments, we choose
p-biphenylyl azide 4 because both the corresponding nitrene
528,29 and the expected nitrenium cation 62,4 (Scheme 2) are well
characterized. We will then proceed to extend this approach to
o-biphenylyl azide 7 and 1-naphthyl azide 14 which produce
short-lived singlet arylnitrenes and hitherto unknown nitrenium
cations.
Similarly, Michalak et al. produced fluorinated arylnitrenium
cations in acidic acetonitrile solution by flash photolysis of the
corresponding aryl azides.26
Although product studies indicate that the parent singlet
phenylnitrene (τ ≈ 1 ns, organic solvents) can also be protonated
in acidic aqueous solution, LFP studies failed to produce the
(23) Srivastava, S.; Toscano, J. P.; Moran, R. J.; Falvey, D. E. J. Am. Chem.
Soc. 1997, 119, 11552-11553.
(24) Srivastava, S.; Ruane, P. H.; Toscano, J. P.; Sullivan, M. B.; Cramer, C.
J.; Chiapperino, D.; Reed, E. C.; Falvey, D. E. J. Am. Chem. Soc. 2000,
122, 8271-8278.
(27) Fishbein, J. C.; McClelland, R. A. Can. J. Chem. 1996, 74, 1321-1328.
(28) Burdzinski, G. T.; Gustafson, T. L.; Hackett, J. C.; Hadad, C. M.; Platz,
M. S. J. Am. Chem. Soc. 2005, 127, 13764-13765.
(25) Zhu, P.; Ong, S. Y.; Chan, P. Y.; Poon, Y. F.; Leung, K. H.; Phillips, D.
L. Chem. Eur. J. 2001, 7, 4928-4936.
(29) Burdzinski, G.; Hackett, J. C.; Wang, J.; Gustafson, T. L.; Hadad, C. M.;
Platz, M. S. J. Am. Chem. Soc. 2006, 128, 13402-13411.
(26) Michalak, J.; Zhai, H. B.; Platz, M. S. J. Phys. Chem. 1996, 100, 14028-
14036.
(30) Hayes, J. C.; Sheridan, R. S. J. Am. Chem. Soc. 1990, 112, 5879-5881.
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A R T I C L E S
Scheme 2
Wang et al.
Scheme 3
Scheme 4
time constant of 11.5 ps (Supporting Information, Figure S1).
The singlet nitrene decay in 88% formic acid is on the time
scale of vibrational cooling of the nitrene in acetonitrile.28,29
Thus, it is possible that it is the vibrationally excited, rather
than the thermalized singlet nitrene, which undergoes protona-
tion. In 88% formic acid, nitrenium cation 6 has a lifetime of
50 ns.
McClelland et al. ruled out azide excited states as the
precursors of the nitrenium cations based on the fact that the
quantum yields of decomposition of the azides remain un-
changed over a 20% to 90% acetonitrile-water mixture, in spite
of a decrease in the yield of the nitrenium cations at higher
acetonitrile concentration.4 Consequently, they assigned the
singlet nitrene as the precursor of the nitrenium cations. The
direct evidence provided in this work confirms that nitrenes are
the precursors of nitrenium cations, as first proposed by the
McClelland group.2,4
2.1.2. Matrix Isolation Spectroscopy and Calculations. The
photochemistry of p-biphenylyl azide in a pure Ar matrix is
very similar to that of parent phenyl azide:30,35 After initial 254
nm photolysis with a low-pressure Hg lamp, a broad band
between 390 and 540 nm is formed, indicating the presence of
the triplet nitrene 5 (green trace b in Figure 2). On subsequent
photolysis at λ > 515 nm, the nitrene undergoes ring expansion
to form the corresponding azepine derivative (cf., Scheme 2).
In all cases the IR spectra calculated for the presumed structures
are in excellent agreement with the experimental IR spectra
(Supporting Information, Figure S2).
2. Results and Discussion
2.1. p-Biphenylylnitrenium Cation.
2.1.1. Ultrafast Spectroscopy. Ultrafast LFP (270 nm) of
p-biphenylyl azide in a mixture of 50% water and 50%
acetonitrile produces the spectra shown in Figure 1. A transient
absorption band centered at 350 nm, which is assigned to singlet
p-biphenylylnitrene 15, is formed within 1 ps. This is in excellent
agreement with our previous observation28,29 of the same nitrene
in acetonitrile. This singlet nitrene, like all other singlet
arylnitrenes,10 has an open-shell electronic structure.31,32 As 15
decays, a peak centered at 465 nm is formed, with an isosbestic
point at 380 nm. On the basis of McClelland’s work,2,4 the newly
formed 465 nm band is assigned to p-biphenylylnitrenium cation
6. This nitrenium ion has a closed-shell singlet ground state.33,34
The rate of formation of the 465 nm band is too slow to be
determined accurately with our spectrometer, and our best
estimation of this time constant is around 3 ns. If the photolysis
is performed in 88% formic acid, the decay rate of singlet
p-biphenylylnitrene and the formation rate of its corresponding
nitrenium cation are identical within experimental error, with a
Introduction of 30% HCl in the Ar matrix profoundly changes
the photochemistry. The nitrene and the resulting azepine spectra
are no longer observed. Instead, a different, intense band
centered at 460 nm rises under the same conditions of photolysis
(red trace c in Figure 2). This newly formed band is assigned
to p-biphenylylnitrenium cation 6, consistent with the work of
McClelland’s LFP studies4 and the transient spectra described
above.
(31) Kim, S. J.; Hamilton, T. P.; Schaefer, H. F., III. J. Am. Chem. Soc. 1992,
114, 5349-5355.
(32) Hrovat, D. A.; Waali, E. E.; Borden, W. T. J. Am. Chem. Soc. 1992, 114,
8698-8699.
(33) Cramer, C. J.; Dulles, F. J.; Falvey, D. E. J. Am. Chem. Soc. 1994, 116,
9787-9788.
(35) Bally, T. In ReactiVe Intermediate Chemistry; Moss, R. A., Platz, M. S.,
Jones, M., Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, 2004; pp 797-
(34) Cramer, C. J.; Falvey, D. E. Tetrahedron Lett. 1997, 38, 1515-1518.
845.
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Ultrafast Spectroscopy of Arylnitrenium Cations
A R T I C L E S
Table 1. Excited States and Oscillator Strength for
p-Biphenylylnitrenium Cation 6 Calculated by the CASSCF and
CASPT2 Methods
oscillator
CASSCF/eVa
CASPT2/eVb
CASPT2/nm
strength
excitations/%c
(0.00)
2.42
3.60
4.13
(0.00)
2.28
2.52
3.23
74% ground config
545
493
384
1.2 × 10-2 66% (H-1 f L)
5.4 × 10-1 53% (H f L)
4.0 × 10-2 38% (H-2 f L)
+ 25% (H-2 f L +
H f L)
4.97
5.06
5.41
3.75
4.16
3.93
330
298
315
2.1 × 10-1 highly mixed
1.2 × 10-1 highly mixed
6.6 × 10-2 highly mixed
Figure 1. Transient spectra produced by ultrafast photolysis of p-biphenylyl
azide 4 in acetonitrile-water (50% vs 50%) mixture. The spectra were
generated by ultrafast LFP (270 nm) with a time window of 15-2500 ps.
a Active space comprises 10 electrons in 10 π orbitals, ground state
energy: -514.557109 hartree. b Ground state energy: -516.086437 hartree.
c Main excitations in the CASSCF wave function, where H ) HOMO and
L ) LUMO.
steric hindrance of the ortho hydrogen atoms means that
planarity is not reached in p-biphenylylnitrenium cation, in spite
of the stronger inter-ring double-bond character.
At the optimized geometry, the excited states were calculated
by the CASPT2 method, based on a reference CASSCF wave
function with an active space comprising 10 electrons in 10
orbitals. The orbitals which are involved mainly in the excita-
tions that lead to the observed bands of 6 are listed in Table 1
and shown in Figure S4 of the Supporting Information. The
first excitation, predicted at 545 nm, corresponds mainly to
HOMO f LUMO electron promotion but, owing to poor
overlap between the ground state and the excited-state wave
function, the transition moment is small. The following excita-
tion, predicted at 493 nm, is composed of a 53% HOMO f
LUMO excitation. The intensity of this band is higher because
of greater overlap of the MOs between which the electronic
promotion occurs. Higher excitations are predicted with a lower
intensity, and all of them are of mixed character involving
mainly excitations to the π-LUMO. As a result of the essentially
nonbonding character of the LUMO, promoting electrons into
higher virtual orbitals requires more energy than promoting them
from lower occupied MOs to the LUMO.
Figure 2. (a) UV-vis spectrum of p-biphenylyl azide 4 in an Ar matrix;
(b) after photolysis at 254 nm; (c) after photolysis at 254 nm in the presence
of 30% HCl in Ar; (d) after bleaching at λ > 590 nm.
Scheme 5
The quantitative accord of the CASPT2 calculations (red bars
in Figure 2) with experiment is satisfactory, and the main strong
band, mainly due to HOMO f LUMO excitation, is well
reproduced.
The corresponding IR spectra (Figure 3), recorded under the
same conditions of photolysis as the UV-vis spectra in Figure
2 (red trace), show some peaks that increase after the first
irradiation at 254 nm (spectrum b) and decrease on bleaching
the photoproduct at λ > 590 nm (spectrum c). Dashed lines
associate these bands with peaks in the calculated spectrum a
of the p-biphenylylnitrenium cation. The position and relative
intensity of most of the bands are reproduced reasonably well
by the B3LYP calculations (spectrum a in Figure 3), but accord
with experiment is somewhat lacking because some important
calculated bands are missing in the experimental spectrum.
Calculations were performed to describe the nature of the
electronic excitations responsible for the observed absorption.
The geometry of the closed-shell singlet ground state of
p-biphenylylnitrenium cation33,34 was optimized by B3LYP/6-
31G(d) (Supporting Information, Figure S3). The singlet-triplet
gap of this ion was not calculated in this study, but analogous
values have been reported by Cramer and co-workers.33,34 The
two phenyl moieties were found to be twisted by 19.5°, in good
agreement with the dihedral angle 17.6° reported by Zhu et al.25
The presence of the NH+ substituent changes the electronic
structure of the molecule. In particular, the weight of the VB
resonance structures which maintain a double bond between the
two phenyl groups increases sensibly (Scheme 5 and Supporting
Information, Figure S3) thus favoring planarization of the
biphenylylnitrenium cation. However, the increased double-bond
character between the two phenyl rings also leads to a shortening
of the inter-ring distance by 0.045 Å, and the resulting additional
A possible origin of the poor matching may be the significant
increase of the polarity of the medium containing the cation,
caused by the presence of HCl in the matrix. Hence, interaction
with the solvent, not considered in the calculations, could acquire
significant importance in correctly describing the force field of
the molecule. In particular, the resulting IR spectrum could have
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A R T I C L E S
Wang et al.
Figure 4. Transient spectra produced by ultrafast photolysis of o-biphenylyl
azide 7 in 88% formic acid. The spectra were generated by ultrafast LFP
(270 nm) with a time window of 2-20 ps.
Figure 3. (a) IR spectrum of 6 calculated by B3LYP/6-31G*; (b) IR
spectrum produced by bleaching of p-biphenylyl azide 4 in Ar/HCl at 254
nm (negative peaks) and formation of the nitrenium cation 6 (positive peaks);
(c) bleaching of 6 by irradiation at λ > 590 nm (negative peaks).
some shifts in the positions and in the intensities of some bands,
while the general pattern could still be maintained.
The IR spectra do not reveal what happens upon bleaching
of 6, because no major bands rise in the process (blue trace c
in Figure 3). A possibility is that on photoexcitation 6 reacts
with the neighboring chloride anion, as was posited by McIlroy
et al. in the case of the diphenylnitrenium cation, which was
found to react with Cl- near the diffusion limit,36 or that it gives
its proton back to Cl-.
2.2. o-Biphenylylnitrenium Cation.
2.2.1. Ultrafast Spectroscopy. In acetonitrile, the lifetime
of singlet o-biphenylylnitrene 8 is only 16 ps, because 8 is
deactivated by the extremely rapid formation of azirine 9 and
isocarbazole 1228,29 (see Scheme 3). Hence, highly acidic
conditions are necessary to produce the o-biphenylylnitrenium
cation 11 in competition with the two intramolecular cycliza-
tions.
Ultrafast photolysis (270 nm) of o-biphenylyl azide 7 in 88%
formic acid produces the spectra in Figure 4. A transient
absorption band centered at 400 nm is formed within 1 ps,
which is assigned to singlet o-biphenylylnitrene 8, consistent
with our previous observation28,29 of the same nitrene in
acetonitrile. As singlet o-biphenylylnitrene decays, a peak
centered at 610 nm is formed, with an isosbestic point at 465
nm. By analogy with the prior example of p-biphenylyl azide,
the carrier of the 610 nm band is assigned to o-biphenylylni-
trenium cation 11. The singlet nitrene decay in 88% formic acid
is also on the time scale of vibrational cooling of the nitrenes
in acetonitrile.28,29 Once again it is the vibrationally excited,
rather than the thermalized singlet nitrene, which undergoes
protonation.
Figure 5. (a) UV-vis spectrum of o-biphenylyl azide 7 in Ar; (b) after
short bleaching at 254 nm; (c) after longer bleaching at 254 nm; (d) after
bleaching at 254 nm in the presence of 30% HCl in Ar; (e) after subsequent
bleaching of 11 at λ > 590 nm.
intramolecular decay processes of singlet o-biphenylylnitrene
have the same rates in 88% formic acid as in acetonitrile, we
deduce that the apparent protonation rate constant is 6.7 × 1010
s-1 in 88% formic acid. Based on this assumption, we can also
conclude that 52% of the singlet o-biphenylylnitrene is proto-
nated in this acidic solvent. The carrier of the 610 nm band
shows only very little decay in a 3 ns time window. Its lifetime
of 27 ns in 88% formic acid was determined by ns time-resolved
LFP techniques.
2.2.2. Matrix Isolation. In a pure Ar matrix the first
photoproduct of o-biphenylyl azide, obtained by short UV
photolysis, is the triplet nitrene with its intense peak at 340 nm
and the broad band at 450-550 nm (green trace b in Figure
5).37 This species is extremely photosensitive: on continuing
the same irradiation for a few more minutes, the nitrene attacks
the adjacent ring to eventually form carbazole 13, which can
be readily identified by its group of sharp bands at 300-350
nm (brown trace c in Figure 5).38
Global fitting of the decay at 400 nm and the growth at 610
nm gives a time constant of 7.7 ps (Supporting Information,
Figure S5). In acetonitrile, the lifetime of singlet o-bipheny-
lylnitrene is 16 ps, which is mainly deactivated by intramolecular
cyclization to azirine 9 and isocarbazole 12. Assuming that
(37) Tsao, M.-L.; Gritsan, N.; James, T. R.; Platz, M. S.; Hrovat, D. A.; Borden,
W. T. J. Am. Chem. Soc. 2003, 125, 9343-9358.
(38) Reiser, A.; Willets, F. W.; Terry, G. C.; Williams, V.; Marley, R. Trans.
Faraday Soc. 1968, 64, 3265-3275.
(36) McIlroy, S.; Moran, R. J.; Falvey, D. E. J. Phys. Chem. A 2000, 104,
11154-11158.
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Ultrafast Spectroscopy of Arylnitrenium Cations
A R T I C L E S
Table 2. Excited States and Oscillator Strengths for
o-Biphenylylnitrenium Cation 11 Calculated by the CASSCF and
CASPT2 Methods
oscillator
CASSCF/eVa
CASPT2/eVb
CASPT2/nm
strength
excitations/%c
(0.00)
2.51
2.79
(0.00)
1.18
2.01
79% ground config
658
615
3.6 × 10-1 64% (H f L)
8.5 × 10-3 32% (H-4 f L) +
29% (H-1 f L)
3.31
4.09
4.59
4.77
2.54
2.86
3.50
3.83
489
433
354
324
6.9 × 10-3 highly mixed
5.0 × 10-3 highly mixed
8.4 × 10-3 highly mixed
1.9 × 10-1 highly mixed
a Active space comprises 10 electrons in 10 π orbitals, ground state
energy: -514.541996 hartree. b Ground state energy: -516.080167 hartree.
c Main excitation in the CASSCF wave function, where H ) HOMO and
L ) LUMO.
In addition, the spectrum reveals the presence of the carba-
zolyl radical 13-H• (sharp band at 600 nm), and even of the
radical cation of carbazole, 13+• (sharp band at 850 nm).39 It is
known that aromatic amines can undergo ionization on UV
irradiation.39,40
Figure 6. (a) IR spectrum produced by bleaching of o-biphenylyl azide
in Ar/HCl at 254 nm (negative peaks) and formation of the nitrenium
cation 11 (positive peaks); (b) bleaching of 11 (negative peaks) by
irradiation at λ > 590 nm; (c) IR spectrum of 11 calculated by B3LYP/6-
31G*.
The corresponding IR spectra (Supporting Information, Figure
S6) demonstrate that the formation of carbazole is indeed the
dominant process. However, some small bands which increase
during the first photolysis and decrease after the second
photolysis, dashed lines, appear to be due to the presence of
the nitrene, whose calculated spectrum matches reasonably well
with experiment. In addition, a band in the region of 1900 cm-1
is also present and increases in both photolyses. The only species
which can have this kind of vibrational spectrum is the
keteneimine 10 derived from a ring expansion process (see
Scheme 3). No IR evidence was found for the carbazolyl radical
or the radical cation, which seem to be formed only in small
quantities.
The reactivity of the azide completely changes upon introduc-
ing 30% HCl into the matrix (red trace d in Figure 5). Under
the same conditions of photolysis, a different and much
more intense band rises between 550 and 750 nm, which is
assigned to o-biphenylylnitrenium cation 11 based on the
transient spectra in Figure 4. Again the nitrenium cation can be
bleached by subsequent photolysis at λ > 600 nm (blue trace e
in Figure 5).
Again quantum chemical calculations were performed in order
to describe the absorptions associated with the nitrenium cation
11. In the B3LYP/6-31G(d) geometry (Supporting Information,
Figure S7) the two phenyl moieties are found to be twisted by
28.8°, nearly 50% more than in the p-biphenylylnitrenium
cation, due to the increase of the steric hindrance introduced
by the ortho NH+ substituent. In spite of this, the resonance
structures with an inter-ring double bond seem more predomi-
nant because that bond is slightly shorter (1.435 Å compared
to 1.441 Å of the para isomer, Supporting Information, Figure
S3).
accord with experiment, is again predominantly due to HOMO
f LUMO electron promotion. The following weak transition,
predicted at 615 nm, has an oscillator strength that is more than
10 times smaller, and the CASSCF wave function of the
corresponding excited state is mainly composed of 29%
HOMO-1 f LUMO and 32% HOMO-4 f LUMO excitation.
Thus, the order of the first two excited states is inverted on
going from p- to o-biphenylylnitrenium cation. All the other
excited states in the calculated range are highly mixed, as in
the p-biphenylylnitrenium cation. The major electron promotions
occur again to the LUMO, which, because of its essentially
nonbonding character, lies at very low energy (Supporting
Information, Figure S8).
The corresponding IR spectra (Figure 6) reveal how bands
of the supposed nitrenium cation initially generated (spectrum
a) and subsequently destroyed (spectrum b) are in good
agreement with those of the simulated spectrum (spectrum c),
calculated by the DFT method, although some of the weaker
calculated bands again seem to be missing from the experimental
spectra (cf., discussion on the spectra shown in Figure 3). In
this case it seems that on bleaching of the nitrenium cation, the
nitrene is reformed by deprotonation, although the evidence for
this, admittedly, is not overwhelming.
2.3. 1-Naphthylnitrenium Cation.
2.3.1. Ultrafast Spectroscopy. Ultrafast photolysis (λex
)
270 nm) of 1-naphthyl azide 14 (Scheme 4) in 88% formic acid
produces the spectra shown in Figure 7. A peak centered at
380 nm is formed within 1 ps of the laser pulse. The carrier of
this absorption is assigned to singlet 1-naphthylnitrene 15,
consistent with its previous observation29 in acetonitrile. As
singlet 1-naphthylnitrene decays, a new species is formed, with
an absorption centered at 495 nm and an isosbestic point at
430 nm. The carrier of the 495 nm absorption band is assigned
to 1-naphthylnitrenium cation 17. This is consistent with Kung
and Falvey’s report of the spectrum of the closely related species
N-methyl-N-1-naphthylnitrenium cation.16 This assignment is
At this geometry, CASPT2 calculations were performed to
predict the positions and intensities of the absorption bands of
the nitrenium cation (Table 2 and bars on the bottom of Figure
5). The strong visible transition, predicted at 654 nm, in striking
(39) Brede, O.; Maroz, A.; Hermann, R.; Naumov, S. J. Phys. Chem. A 2005,
109, 8081-8087.
(40) Hiyoshi, R.; Hiura, H.; Sakamoto, Y.; Mizuno, M.; Sakai, M.; Takahashi,
H. J. Mol. Struct. 2003, 661-662, 481-489.
9
J. AM. CHEM. SOC. VOL. 129, NO. 26, 2007 8385

A R T I C L E S
Wang et al.
Figure 7. Transient spectra produced by ultrafast photolysis of 1-naphthyl
azide 14 in 88% formic acid. The spectra were generated by ultrafast LFP
(270 nm) with a time window of 2-20 ps.
Table 3. Excited States and Transition Strengths for
1-Naphthylnitrenium Cation 17 Calculated by the CASSCF and
CASPT2 Methods
Figure 8. (a) UV-vis spectrum of 1-napththyl azide 14 in Ar;
(b) after bleaching at 254 nm; (c) after bleaching at 254 nm in the
presence of 30% HCl in Ar; (d) after subsequent bleaching of 17 at λ >
475 nm.
oscillator
CASSCF/eVa
CASPT2/eVb
CASPT2/nm
strength
excitations/%c
(0.0)
2.48
2.99
4.36
(0.00)
2.32
2.36
3.90
69% ground config
to the corresponding nitrene. Schrock and Schuster performed
nanosecond time-resolved LFP of 1-naphthyl azide in benzene,
obtaining direct evidence by transient spectroscopy of the
corresponding triplet nitrene, which eventually forms 1,1′-
azonaphthalene.43 Recently, Maltsev et al.44 reported a more
extensive matrix UV-vis and IR study of the photochemistry
of 1-naphthyl azide in argon, and the singlet surface of
1-naphthylnitrene was studied by modern computational tech-
niques. Tsao and Platz used LFP with IR detection to directly
observe the benzazirine intermediate.45 Its lifetime (2.3 µs) was
in excellent agreement with the value deduced by Schrock and
Schuster.43
535
526
318
9.7 × 10-4 54% (H-1 f L)
4.3 × 10-3 55% (H f L)
1.7 × 10-3 21% (H-2 f L)
+ 16% (2*H f L)
+ 13% (H-3 f L)
4.59
5.24
5.60
4.05
4.77
4.44
306
260
279
1.8 × 10-3 highly mixed
2.9 × 10-3 highly mixed
6.1 × 10-3 highly mixed
a Active space comprises 10 electrons in 10 π orbitals, ground state
energy: -437.670042 hartree. b Ground state energy: -438.931647 hartree.
c Main excitation in the CASSCF wave function, where H ) HOMO and
L ) LUMO.
also consistent with CASPT2 calculations (Table 3). Thus, there
is little doubt that this assignment is correct.
In our experiment, after a first irradiation of 1-naphthyl azide
at 254 nm the previously reported spectrum of 315 is observed
(green trace b in Figure 8, sharp 540 nm band). Further
photolysis leads initially to azirine 16, which opens to seven-
membered ring products, as described in detail in ref 25.
In a matrix containing 30% HCl, the spectrum obtained after
initial UV photolysis with a low-pressure Hg lamp has a
completely different shape characterized by an intense broad
absorption in the region between 400 and 650 nm (red trace c
in Figure 8). The band can be bleached by irradiation at λ >
475 nm (blue trace d in Figure 8). The electronic excitations of
the 1-naphthylnitrenium cation predicted by a CASPT2 calcula-
tion (red bars in Figure 8 and Table 3), and the transient spectra
shown in Figure 7, secure the assignment of the 500 nm band
to the nitrenium cation. As mentioned earlier, Kung and Falvey16
reported the solution-phase spectrum of the closely related
species, N-methyl-N-1-naphthylnitrenium cation with a broad
band centered at 500 nm. This is further evidence that we
have succeeded in forming and detecting 1-naphthylnitrenium
cation.
Global fitting of the decay at 380 nm and the growth at 495
nm gives a time constant of 8.4 ps (Supporting Information,
Figure S9). In acetonitrile, the lifetime of singlet 1-naphthylni-
trene (12 ps) is mainly limited by intramolecular cyclization to
azirine 16 (Scheme 4). If we make the same assumption as in
the case of o-biphenylyl azide, assuming the formation of azirine
has the same rate in 88% formic acid as in acetonitrile, the
apparent protonation rate constant is 3.6 × 1010 s-1 in 88%
formic acid. Therefore, we can also conclude that 30% of the
singlet 1-naphthylnitrene is protonated in this solvent. As before,
it is the vibrationally excited, rather than the thermalized singlet
nitrene, which undergoes protonation. The lifetime of 1-naph-
thylnitrenium cation is only 860 ps (Supporting Information,
Figure S10), which explains why this species cannot be observed
by nanosecond time-resolved LFP methods.
2.3.2. Matrix Isolation. The photolysis of 1-naphthyl azide
in a pure Ar matrix was first studied by Dunkin and Thomson,41
who conjectured that the initially formed 1-naphthylnitrene
produces azirine 16 and that the azirine can be subsequently
converted to the keteneimine by further irradiation. Reiser et
al.42 irradiated the azide in an organic glassy matrix at 77 K
and recorded the optical spectra of the products. They reported
absorption bands at 223, 367, and 536 nm that they attributed
For this molecule, the first excitation is characterized by
HOMO-1 f LUMO electronic promotion. In the second excited
state the HOMO f LUMO electronic transition contributes with
a weight of 55% to the CASSCF wave function (Table 3).
Despite the change from a biphenylyl to a naphthyl group, the
(41) Dunkin, I. R.; Thomson, P. C. P. J. Chem. Soc., Chem. Commun. 1980,
(43) Schrock, A. K.; Schuster, G. B. J. Am. Chem. Soc. 1984, 106, 5234-5240.
(44) Maltsev, A.; Bally, T.; Tsao, M.-L.; Platz, M. S.; Kuhn, A.; Vosswinkel,
M.; Wentrup, C. J. Am. Chem. Soc. 2004, 126, 237-249.
499-501.
(42) Reiser, A.; Bowes, G.; Horne, R. J. Trans. Faraday Soc. 1966, 62, 3162-
3169.
(45) Tsao, M.-L.; Platz, M. S. J. Phys. Chem. A 2004, 108, 1169-1176.
9
8386 J. AM. CHEM. SOC. VOL. 129, NO. 26, 2007

Ultrafast Spectroscopy of Arylnitrenium Cations
A R T I C L E S
p-biphenylyl azide, 19 °C for o-biphenylyl azide, and -27 °C for
1-naphthyl azide. Photolysis of the azides was performed with a
low-pressure Hg lamp, whereas for the bleaching of the nitrenium
cations a high-pressure Hg/Xe arc was used with 590 nm or 475 nm
cutoff filters (cf., captions of figures). Electronic absorption spectra
were recorded on
a Perkin-Elmer Lambda 900 spectrometer
(200-1000 nm). IR spectra were measured on a Bomem DA3
interferometer (4000-500 cm-1) with a mercury cadmium telluride
(MCT) detector.
3.3. Computational Chemistry. The geometries and harmonic
vibrational frequencies of the three nitrenium cations (6, 11, and 17)
were calculated by the B3LYP density functional method46,47
using the 6-31G(d) basis set, with the Gaussian 03 suite of programs.48
All equilibrium structures were ascertained to be minima on the
potential energy surfaces. The harmonic frequencies were scaled
by a factor of 0.96 for their use in assigning the experimental IR
spectra.49
Excited-state energies of the nitrenium cations were calculated at
the above geometries by the CASSCF/CASPT2 procedure50,51 with the
ANO-S basis set of Pierloot et al.52 using the MOLCAS program.53 In
order to arrive at a satisfactory description of all excited states at the
CASPT2 level (i.e., remove intruder states) it was necessary to resort
to the level-shifting technique,54 whereby it was carefully ascertained
that no artifacts are introduced.
3.4. Ultrafast Spectroscopy. Details of the ultrafast time-resolved
spectrometer in use at The Ohio State University Center for Chemical
and Biophysical Dynamics have been reported elsewhere.29
Figure 9. (a) IR spectrum of 17 calculated by B3LYP/6-31G*; (b) IR
spectrum produced by bleaching of 1-naphthyl azide 14 in Ar/HCl
at 254 nm (negative peaks) and formation of the nitrenium cation 17
(positive peaks); (c) bleaching of 17 (negative peaks) by irradiation at λ >
475 nm.
4. Conclusions
LUMO maintains an essentially nonbonding character, favoring
excitations from filled orbitals to the LUMO (Supporting
Information, Figure S11).
The lifetimes of certain singlet arylnitrenes at ambient
temperature are too short to allow for their protonation to form
the corresponding nitrenium cations on the nanosecond time
scale. We have shown using ultrafast time-resolved flash
photolysis methods that two such nitrenium cations can be
conveniently generated from p- and o-biphenylyl and 1-naphthyl
azides in 88% formic acid. In this solvent, o-biphenylyl (τ )
7.7 ps) and 1-naphthylnitrene (τ ) 8.4 ps) are protonated and
converted to nitrenium cations. In many respects, 88% aqueous
formic acid is the ideal solvent for direct detection of mono-
substituted arylnitrenium cations. The azide precursors
dissolve readily and have sufficient stability in this solvent for
photochemical studies, and the corresponding nitrenes are
readily protonated, and the resultant nitrenium ions have
relatively long lifetimes in this solvent. These experiments show
also that the singlet nitrenes, rather than the excited states of
the azides, are the direct precursors of the nitrenium cations as
first proposed by McClelland et al.4 These same nitrenes can
be protonated in argon/HCl matrices to form persistent nitrenium
cations which can be characterized by both electronic and
vibrational spectroscopy and whose spectra are in excellent
agreement with the predictions of theory. These two approaches
In Figure 9, the calculated IR spectrum of 1-naphthylnitre-
nium cation (spectrum a) is correlated with a series of bands
which are generated by the initial photolysis at 254 nm of 14
in an Ar matrix containing 30% HCl (spectrum b) and bleached
by the second irradiation (λ > 475 nm, spectrum c). The
agreement with experiment (dashed lines in Figure 9) is
satisfactory and seems to leave little doubt about the identity
of the species obtained. However, the identity of the species
formed upon bleaching is again not revealed by the IR
spectrum which shows interesting unassigned bands at 1600-
1700 cm-1
.
Nevertheless we note some disagreement between the ex-
perimental spectra, in particular in the case of the naphthylni-
trenium cation 17 where some major experimental bands,
e.g., the pair between 1620 and 1700 cm-1, are not predicted
to occur. We believe that this may be due to (a) photoprotonation
of 15 at the aromatic ring, rather than at the N-atom, or (b)
attachment of the chloride anion to the aromatic ring, as was
found to occur in nitrenium cations obtained by photolysis of
aminopyridinium cations.24 We are currently exploring these
possibilities.
(46) Lee, C.; Yang, W.; Parr, R. G. Phys. ReV. B: Condens. Matter 1988, 37,
785-789.
(47) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
(48) Frisch, M. J.; et al. Gaussian 03, revision C.01; Gaussian, Inc.: Wallingford,
CT, 2005.
3. Experimental Section
3.1. Synthesis. The syntheses of the azides used in this work have
been previously reported.1-4,37,45
(49) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502-16513.
(50) Roos, B. AdV. Chem. Phys. 1987, 69, 399-445.
(51) Andersson, K.; Roos, B. O. In AdVanced Series in Physical Chemistry;
1995; Vol. 2, pp 55-109.
3.2. Matrix Isolation Spectroscopy.35 A few ground crystals of
azides were placed in a U-tube attached to the inlet system of a closed-
cycle cryostat. A mixture of argon (Carbagas, 99.995%) with 10%
nitrogen (Carbagas, 99.995%) was flowed through the U-tube and
slowly deposited on a CsI window (UV transparent quality, Korth
Kristalle GmbH) maintained at ca. 20 K. In the protonation
experiments, 30% dry gaseous HCl was added to the mixture. During
deposition the temperature of the U-tube was kept at 14 °C for
(52) Pierloot, K.; Dumez, B.; Widmark, P.-O.; Roos, B. O. Theor. Chim. Acta
1995, 90, 87-114.
(53) Andersson, K.; Blomberg, M. R. A.; Fu¨lscher, M. P.; Kello¨, V.; Lindh, R.;
Malmqvist, P.-Å.; Noga, J.; Olson, J.; Roos, B. O.; Sadlej, A.; Siegbahn,
P. E. M.; Urban, M.; Widmark, P.-O. MOLCAS, version 5. University of
Lund, 2002.
(54) Roos, B. O.; Andersson, K.; Fuelscher, M. P.; Serrano-Andres, L.; Pierloot,
K.; Merchan, M.; Molina, V. THEOCHEM 1996, 388, 257-276.
9
J. AM. CHEM. SOC. VOL. 129, NO. 26, 2007 8387

A R T I C L E S
Wang et al.
expand the range of monoarylnitrenium cations which can be
formed by protonation of singlet arylnitrenes.
J.W. thanks the Ohio State University Graduate School for a
Presidential Fellowship.
Supporting Information Available: Complete ref 48, kinetic
traces for global fitting, matrix IR spectroscopies, and the
calculated molecular geometries and orbitals (Figures S1-S11).
This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgment. Support of this work in Columbus by the
National Science Foundation and the Ohio Supercomputer
Center and in Fribourg by the Swiss National Science
Foundation (Project No. 200020-113268) is gratefully acknowl-
edged. G.B. is a holder of a “Homing” Grant from the
Foundation for Polish Science (FNP) in the year 2007.
JA071325J
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8388 J. AM. CHEM. SOC. VOL. 129, NO. 26, 2007