J. Am. Chem. SOC.1981, 103, 822-829
822
Absorption Spectra and Rearrangements of Halotoluene Parent Cations in Solid Argon Brian W. Keelan and Lester Andrews* Contribution from the Chemistry Department, University of Virginia, Charlottesuille, Virginia 22901. Received February 25, 1980
Abstract: Matrix photoionization of dilute fluorotoluene samples produced relatively sharp photosensitive absorptions in good agreement with gas-phase photodissociation spectra for ring-substituted fluorotoluene parent cations. The benzyl chloride parent cation form was observed as a sharp, photosensitive 469.3 nm band in both benzyl chloride and pchlorotoluene experiments, whereas chlorotoluene cations gave broad absorptions with little photolysis. Experiments with 0- and p-fluorotoluene produced parent cation absorptions, which were considerably sharper than the gas-phase PDS, and the matrix absorptions exhibited vibrational structure. Benzyl and substituted benzyl radicals were also observed in these experiments.
Introduction Halotoluene parent cations have been studied in the gas phase by mass spectrometric techniques,’” photoelectron spectroscopy (PES),7,8and photodissociation spectroscopy (PDS).8,9 Rearrangement between the benzyl halide and ring-substituted halotoluene structural forms is of particular interest; recent PDS observations with benzyl chloride showed two distinct C7H7C1+ population^.^ Several studies have suggested that ring-expanded halocycloheptatriene cations are intermediates in these isomerization processes. Molecular ions can be produced and trapped in solid argon for absorption spectroscopic and photochemical studies which are complementary to gas-phase work.1° In a recent matrix photoionization study, the toluene parent cation was observed in solid argon at 2.88 eV (430 nm),” in very good agreement with the gas-phase PDS band peak at 2.97 eVS and 3.0-eV difference between the adiabatic first and vertical second ionization energies from the PES.7 In a following matrix investigation, cycloheptatriene cation was found to rearrange to toluene cation upon visible photolysis.12 The present halotoluene study was undertaken to explore the relationship between gas-phase PDS and matrix absorption spectra and to further examine the rearrangements of the halotoluene parent cations. 134,6
Experimental Section The cryogenic apparatus for optical absorption studies and the windowless argon resonance lamps have been described previously.”J4 The hydrogen resonance lamp consisted of a 12-mm 0.d. Pyrex tube, with a 6-mm 0.d. side arm, vacuum sealed by a I / , in. ultra-torr fitting to the outside of a brass flange with a 1 in. X 2 mm thick diameter MgF, window sealed by an O-ring on the inside, similar to that used by Milligan and Jacox.ls Either 2% or 5% samples of hydrogen in argon were (1) Tait, J. M. S.; Shannon, W.
T.; Harrison, A. G . J . Am. Chem. Soc.
1962, 84,4.
(2) Brown, P. J. Am. Chem. SOC.1968, 90, 4459, 4461. (3) Brown, P.Org. Mass Spectrom. 1970, 3, 639. (4)Yeo, A. N.H.; Williams, D. H. Chem. Commun. 1970, 886. ( 5 ) Jackson, J. A,; Lias, S. G . ;Ausloos, P. J . Am. Chem. Soc. 1977, 99, 7515. (6)Stapleton, B. J.; Bowen, R. D.; Williams, D. H. J . Chem. Soc., Perkin Trans. 2 1979, 1219. (7) Baker, A. D.; May, D. P.;Turner, D. W. J . Chem. SOC.B 1968, 22. (8) Dymerski, P.P.; Fu, E. W.; Dunbar, R. C. J . Am. Chem. SOC.1974, 96, 4109. (9) Fu, E.W.; Dymerski, P. P.; Dunbar, R. C. J . Am. Chem. Soc. 1976, 98, 337. (10) Andrews, L. Annu. Rev. Phys. Chem. 1979, 30, 79. (11) Andrews, L.; Miller, J. H.; Keelan, B. W. Chem. Phys. Lett. 1980, 71, 207. (12) Andrews, L.; Keelan, B. W. J . Am. Chem. Soc. 1980, 102, 5732. (13) Andrews, L. J . Chem. Phys. 1975, 63, 4465. (14) Andrews, L.;Tevault, D. E.; Smardzewski, R. R. Appl. Spectrosc. 1978, 32, 157. (15) Milligan, D. E.;Jacox, M. E. J . Chem. Phys. 1974, 47, 5146.
0002-7863/81/1503-822$01,00/0
pumped through the tube and excited by a microwave discharge. Samples of benzyl fluoride,p-, 0-,and m-fluorotoluene,benzyl chloride, p , 0-,and m-chlorotoluene, benzyl bromide, and p-bromotoluene (all Aldrich) were distilled from glass beads following outgassing and then diluted with argon to matrix/reactant (M/R = 100/1,200/1, 300/1, or 400/1). A sample of benzyl chloride-d, was synthesized by photolysing toluene-d8 (Merck, Sharpe and Dohme) vapor (20 torr) and CI2(26 torr) in a 2-L Pyrex bulb for 2 h which formed liquid on the bulb wall. The product was cooled to -63 “C and evacuated for 60 min to remove C1, and most of the unreacted toluene. Prior to sample preparation, the bulb was evacuated at room temperature for 1 min to remove the last traces of toluene; dilution with argon produced an M/R = 100/1 sample. Samples were condensed at about 1 mM/h for 3-5 h on a sapphire window at 20 K (argon resonance photoionization experiments) or 12 K (hydrogen resonance photoionization studies). In the argon resonance photoionization experiments, simultaneous irradiation and argon deposition from the windowless discharge tube caused the final sample concentrations in the matrix to be roughly half that of the original sample. The hydrogen resonance lamp was used only afrer sample deposition, generally 10 min of irradiation per hour of sample deposition followed by more sample and more irradiation in turn. All species produced with this technique were formed in a “cold” matrix that allowed little fragment mobility. Spectra were taken with a Cary 17 spectrophotometer from 800 nm down to the parent absorptions,generally near 270 nm. Samples of the precursors were deposited without discharge radiation to determine precursor absorptions. Photolyses were performed with a high-pressure mercury arc (1000-W, BH-6-1, Illumination Industries, Inc.) by using an ultraviolet mirror and Corning glass cutoff filters. High-resolution spectra were recorded at 0.2 nm/s and 3 nm/in before and after each photolysis. Band positions reported to 0.1 nm are accurate to fO.1 nm; others are accurate to k0.5 nm.
Results Matrix photoionization experiments performed with fluoro-, chloro-, and bromotoluenes will be described. Fluorotoluenes. The optical spectrum of a 1% benzyl fluoride-argon sample subjected to continuous argon resonance irradiation from an 8-mm i.d. orifice discharge tube is shown in Figure la. A broad 442-nm band ( A = 0.005) was destroyed by 10 min of 420-nm photolysis, while a 437.9-nm absorption ( A = 0.010) was substantially decreased; 30 min more of 420-nm photolysis destroyed the latter feature, as shown in Figure 1b. Absorptions at 449.6 and 430 nm resisted even full-arc photolysis. The photolysis behavior of the strong sharp band a t 310.4 nm with satellite features at 305.2, 301.0, and 297.7 nm could not be determined due to light scattering by the sample. The spectrum from a p-fluorotoluene experiment, shown in Figure IC, contained a series of absorptions at 437.9 ( A = 0.09), 431.5 ( A = 0.01), and 423.5 nm ( A = 0.02) which were destroyed by 420-nm light, as indicated in Figure Id. The strong 437.9-nm absorption bandwidth is 104 cm-’ at half-maximum. A band at 329.8 nm was destroyed by full-arc photolysis, whereas bands at 465.4, 308.0, 303.5, and 296.2 nm were unaffected by the photolyses. A hydrogen resonance photolysis experiment yielded only the 437.9 ( A = 0.005) and 308.0 nm ( A = 0.01) absorptions. The 0 1981 American Chemical Society
J. Am. Chem. SOC.,Vol. 103, No. 4, 1981 823
Spectra of Halotoluene Cations in Solid Argon
W A V E L E N G T H (nm)
Figure 1. Absorption spectra of fluorotoluene samples subjected to argon resonance photoionization from windowless lamp during condensation. (a) Ar/benzyl fluoride = 100/1 after deposition and (b) after 40 min of 420-1000-nm photolysis. (c) Ar/p-fluorotoluene = 100/1 after condensation and (d) after 30 min of 420-1000-nm photolysis. Dashed trace shows changes after 220-1000 nm photolysis. Table I. Absorptions (nm) and Intensities (Absorbance Units) Observed in Fluorotoluene Experimentsa benzyl fluoride
p-fluorotoluene
absorptns 449.6 44 2 437.9
(I, 1 (0.005) (0.005) (0.010)
I1
If
0.005 0.000 0.000
0.005 0.000 0.000
IDb B AFT PFT
430
(0.01)
0.01
0.01
?
310.4 305.2 301.0 297.1
(0.38) (0.01) (0.10) (0.08)
C
c
C
C
B B B B
C
C
C
c
absorptns 465.4
(I, 1 (0.01)
0.01
If 0.01
IDb PFB
431.9 431.5 423.5 329.8 326 322 308.0 303.5 296.2
(0.090) (0.015) (0.024) (0.08) i0.02j 10.02) io. i 4 j (0.04) (0.03)
0.01 0.00 0.00 0.08 0.02 0.02 0.14 0.04 0.03
0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.14 0.03
PFT PFT PFT R R R PFB PFB PFB
I1
(I,) indicates product band absorbance units, Z1 is after 42(1 or 380-nm photolysis, Ifis after final full-arc photolysis, and ID denotes identification. B denotes benzyl radical, PFB denotesp-fluorobenzyl radical, and R denotes another type of free radical discussed in the test. Not recorded.
new absorptions observed in a-and p-fluorotoluene experiments are summarized in Table I. The spectrum from a second p-fluorotoluene study, compared in Figure 2 with spectra from the other ring-substituted isomers, is almost identical with the first study. This sample was subjected to 500-nm photolysis for 30 min which caused no changes in the absorptions; 420-nm photolysis had the same effect listed in Table
I. Photolysis with 290-nm cutoff light eliminated the last trace of 437.9-nm absorption and halved the 330-nm band system without affecting the 308-nm system. As before the 330-nm band was destroyed and the 308-nm absorption was not changed by full-arc irradiation. Another p-fluorotoluene experiment was done in krypton by using krypton discharge radiation for a 3-h period, and the
Keelan and Andrews
824 J . Am. Chem. Soc.. Vol. 103, No. 4, 1981 Table 11. AbsorDtions (nm) and Intensities (Absorbance Units) Observed in Fluorotoluene Experiments"
m-flu or otolu ene
o-fluorotoluene
absorptns
(1,)
I1
If
IDb
absorptns
(I,)
I1
If
IDb
459.1 450.8 444.5 429.5 416.6 326.0 311.7 309.0 305.0 300.8 298.2
(0.026) (0.005) (0.010) (0.026) (0.008) (0.06) (0.27) (0.14) (0.08) (0.12) (0.11)
0.020 0.004 0.008 0.005
0.036 0.004 0.008 0.000 0.000 0.00 0.16 0.08 0.04 0.06 0.05
OFB OFB OFB OFT OFT
464.2 454.8
(0.007) (0.002)
0.014 0.004
0.014 0.004
MFB MFB
444 437.9 318.4 3 10.5 307.8
(0.004) (0.006) (0.010) (0.030) (0.015)
0.000
0.000 0.000 0.000 0.06 0.03
MFT' PFT'
0.000 0.06 0.20 0.10 0.06 0.08 0.07
R
OFB OFB OFB OFB OFB
0.004 0.010 0.06 0.03
R
MFB MFB
a (I,) indicates product band absorbance units, I1 is after 420- or 380-nm photolysis, If is after final full-arc photolysis, and ID denotes identification. OFB and MFB denote the o- and m-fluorobenzyl radical isomers. R denotes another type of free radical discussed in the text.
spectrum is illustrated in Figure 2a. The product absorptions were red-shifted 2-4 nm from their argon matrix counterparts, and the relative yields of the several product species were altered. The 441.8-nm band was reduced to 20% of its 437.9-nm argon matrix counterpart whereas the 332.5-nm band was doubled and the 467-, 310.3-, 305.7-, and 298.2-nm bands were increased fourfold over their argon matrix counterparts. Two experiments were performed with meta isomer and two with the ortho isomer; product bands and intensities are given in Table 11. The o-fluorotoluene experiments gave band patterns and photolysis behavior similar to the para isomer. New bands at 429.5 ( A = 0.026) and 416.6 nm ( A = 0.008) were virtually destroyed by 380-nm photolysis, as shown in Figure 2c. A new 326.0-nm absorption was destroyed by 220-nm photolysis whereas new band systems beginning at 459.1 and 3 11.7 nm were decreased 20% by 380-nm irradiation and another 20% by the full arc. The m-fluorotoluene studies gave lower product yields. A new weak 444-nm ( A = 0.004) band was destroyed upon 420-nm photolysis that reduced a 437.9-nm band, Figure 2d. A new 318.4-nm feature was unaffected by 420-nm light but destroyed by the full arc. New bands at 464.2, 454.8, 310.5, and 307.8 nm were doubled by 420-nm photolysis and unchanged upon exposure to the full arc. Chlorotoluenes. The spectrum after argon resonance irradiation of a benzyl chloride (a-chlorotoluene) sample (Ar/C7H7Cl = 100/1) during deposition is shown in Figure 3a. New product bands at 707.8 (absorbance = A = 0.15), 664.7 ( A = 0.010), 469.3 ( A = 0.15), 463.7 ( A = 0.01), 452.7 ( A = 0.03), 449.5 ( A = 0.01), and 447.3 nm ( A = 0.01) were destroyed on full-arc (2201000-nm) photolysis, as illustrated in the dashed trace in Figure 3a, which revealed broad bands at 453 and 467 nm. The strong 469.3-nm absorption bandwidth is 68 cm-' at half-maximum. Bands at 314.7 and 302 nm were each reduced by full-arc photolysis, whereas the dominant absorption in this region at 310.4 nm was unaffected. The product bands and absorbances in this benzyl chloride experiment are listed in Table 111. Two other similar experiments produced the sharp 469.3-nm band ( A = 0.10) and the sharp structure on the short wavelength side, and the 664.7- and 707.8-nm bands with the same relative intensities. In one of these studies, photolysis with 520-nm cutoff radiation had no effect on the spectrum, but 420-nm photolysis almost destroyed the 469.3-nm band (to A = 0.01), destroyed the sharp associated structure and the 664.7- and 707.8-nm bands, and produced new absorption at 453 ( A = 0.033) and 467 nm ( A = 0.024); 290-nm photolysis increased the latter bands, 453 (to A = 0.042) and 467 nm (to A = 0.032). In the other experiment, 380-nm photolysis destroyed the red and blue product bands and produced new 453( A = 0.044) and 467-nm ( A = 0.035) absorption, and final photolysis with the full arc reduced both bands, 453 (to A = 0.029) and 467 nm (to A = 0.032). Hydrogen resonance photolysis of an argon/benzyl chloride = 400/1 sample after deposition produced the stronger 469.3-, 463.7-, and 452.7-nm bands, as shown in Figure 3b, with absorptions reduced to 25% of their values produced by continuous argon
Table 111. Absorptions (nm) and Intensities (Absorbance Units) Observed in Chlorotoluene ExperimentB benzyl chloride p-chlorotoluene absorptns (I,) If absorptns (I,) I] If IDb (0.015) 0.00 ACT 707.8 707.8 (0.02) 0.00 (0.010) 0.00 ACT 664.7 664.7 (0.01) 0.00 (0.02) 0.02 0.01 PCT 500
469.3 463.7 452.7 449.5 447.3
(0.15) (0.01) (0.03) (0.01) (0.01)
O.OOc 0.00 O.OOc 0.00 0.00
314.7
(0.04) 0.02
310.4 301.7
(0.09) 0.09 (0.03) 0.02
492 483 415 469.3 463.7 452.7 449 447 3 35 .O 331.0 327.1
(0.04) (0.08) (0.13) (0.12) (0.01) (0.01)
312.7
(0.10)
(w) (w) (0.06) (0.01) (0.01)
0.04 0.02 0.08 0.04 PCT 0.13 0.07 PCT 0.00 ACT+ 0.00 ACT'
ACT+ ACT+ ACT+ 0.06 0.00 R 0.00 0.00 0.00
0.01 0.00 R 0.01 0.00 R b 0.10 0.12 PCB B b
(I,)indicates product band absorbance, I1 is after 420-1000nm photolysis, and If is absorbance after fiial 220-100Gnm photolysis. See text for possible identifications. PCB is pchlorobenzyl radical and B is benzyl radical. Broad 453-nm band remaining after photolysis (A = 0.02) suggests that 452.7nm peak (A = 0.01) on top of 453-nm band represents the change on photolysis; broad 467-nm band (A = 0.02) also remains on photolysis. These broad bands, unique to the benzyl chloride experiments, cannot be identified from the present information.
resonance photolysis. In addition the 708-nm absorption was detected ( A = 0.005), but the 665-nm band was not observed above the noise level in the hydrogen resonance photolysis experiment. The spectrum from a p-chlorotoluene M/R = 100/1 argon resonance experiment is shown in Figure 3c which is similar to the a-chlorotoluene spectrum in many respects. Absorptions observed a t 701.8, 664.7, 469.3, 463.7, and 452.9 nm were not affected by 520-nm photolysis but were destroyed with 420-nm light, as shown in Figure 3d and given in Table 111. An absorption system at 335.0, 331.1, and 327.1 nm and a broad 310-nm band were destroyed upon 220-nm photolysis which more clearly revealed a new 312.7-nm band. Broad bands at 475,481, and 492 nm unique to the p-chlorotoluene study were approximately halved in intensity by 220-nm photolysis. A similar 300/1 experiment gave a reduced yield of the sharp 469.3-nm ( A = 0.08) and the 664.7- and 707.8-nm bands and increased broad bands at 492 ( A = 0.03) and 500 nm ( A = 0.01). Photolysis with 520-1000-nm radiation had no effect on the spectrum; 420-1000-nm light virtually destroyed the sharp 469.3-nm band and the weaker 664.7and 707.8-nm bands and reduced the broad bands by 25%; a final 220-1000-nm photolysis reduced the broad bands to half of their original absorbances. In another experiment with a similar yield
J. Am. Chem. Soc., Vol. 103, No. 4, 1981 825
Spectra of Halotoluene Cations in Solid Argon ,-
c I
1
290
310
-
I
330
A
I
410 W A V E L E N G T H (nm)
I
I
I
430
450
470
Figure 2. Absorption spectra of fluorotoluene cations and fluorobenzyl radicals prepared by matrix photoionization of 1% fluorotoluene samples: (a) krypton, para; (b) argon, para, dashed trace after 30 min of 420-1000-nm photolysis; (c) argon, ortho, dashed trace after 380-1000-nm photolysis; (d) argon, meta, dashed trace after 420-1000-nm photolysis.
of product absorptions, 470-nm cutoff photolysis reduced the 707.8-nm band ( A = 0.009-0.003), the 664.7-nm band ( A = 0.006 to 0.001), and reduced the sharp 469.3-nm absorption ( A = 0.15 to 0.05) and its associated bands. A 380-nm photolysis eliminated the above features without producing any new absorption and decreased the broad 475-nm feature about 20%; final 220-nm photolysis had little additional effect. A hydrogen resonance experiment with p-chlorotoluene, illustrated in Figure 4b, produced a series of broad bands at 500 ( A = 0.01), 492 ( A = 0.02), 483 ( A = 0.02), 475 ( A = 0.03), 468 ( A = 0.02), and 461 nm ( A = 0.01), and broad features were observed at 300 and 310 nm; the sharp 469.3-nm absorption and 665- and 708-nm bands were not observed. Two o-chlorotulene experiments with argon raonance photolysis produced a broad band with maxima at 470 and 480 nm ( A = 0.03), a broad band at 442 nm, a sharp, weak band at 469.3 nm ( A = 0.005), and new absorptions at 327.7 (A = 0.03), 320.7 (A = 0.04), and 310.6 nm ( A = 0.02), which are shown in Figure
4d. Full-arc photolysis halved the broad bands and destroyed the sharp 327.7-nm feature, as illustrated in the dashed trace of Figure 4d. In a similar m-chlorotoluene experiment, a broad band was observed with maxima at 466 and 482 nm, a sharp band appeared at 326.3 nm ( A = 0.20), and weak features were found at 319 and 310 nm as shown in Figure 4c. Photolysis with 290-nm radiation destroyed the 326-nm band and slightly decreased the broad visible bands. Several experiments were performed with a-chlorotoluene-d7 in an attempt to observe deuterium counterparts of the weaker bands above the strong 469.3-nm absorption in C7H7Cl studies. The only product was a sharp band a t 467.8 nm ( A = 0.01) in three experiments; this absorption was decreased 50% by 420-nm photolysis in all three studies. Bromotoluenes. All bromotoluene experiments were done with equilibrium vapor diluted by 100 torr of argon to give approximately 1% gas mixtures, and the argon photolysis experiments employed a 3-mm i.d. orifice discharge tube. The benzyl bromide
J . Am. Chem. SOC.,Vol. 103, No. 4, 1981
Keelan and Andrews 1
1
440
1
1
I
1
460 W A V E L E N G T H ( n m ) m
I
-
-
I
1
\"
I L
