Time-resolved resonance Raman spectra are reported for different concentrations of in cyclohexane solution. The species is observed at low concentrations and it decays on the order of tens of nanoseconds to almost no signal at 100 ns and no other signal is observed up to 15 microseconds. Two species are observed at high concentrations. The first species spectra and lifetime are about the same as that found at low concentration of parent molecule and the second species is a molecular complex observed on the nanosecond to microsecond time scale and formed from bimolecular reaction of iodine atoms with molecules. The chemical reactivity of the species and the molecular complex towards carbon double bonds were investigated using density functional theory calculations. The structure and properties of the species and the molecular complex and their reaction towards ethylene were compared. The species and the both have weak I–I bonds that are the chromophores responsible for similar intense transient absorption bands. However, the geometry of the I–I bond relative to the C–I bond is noticeably different for these two species and this leads to distinctly different chemical reactivity toward carbon double bonds. The isomer readily reacts with ethylene to produce a cyclopropane product and leaving group via a single step and low barrier to reaction while the molecular complex reacts with ethylene to form an ethylene/I intermediate and a leaving group. Probable ramifications for other related molecule–halogen atom complexes are briefly discussed.
REFERENCES
1.
2.
3.
4.
R. M.
Moore
, M.
Webb
, R.
Tokarczyk
, and R.
Wever
, J. Geophys. Res., [Oceans]
101
, 20899
(1996
).5.
J. C.
Mössinger
, D. E.
Shallcross
, and R. A.
Cox
, J. Chem. Soc., Faraday Trans.
94
, 1391
(1998
).6.
C. T.
McElroy
, C. A.
McLinden
, and J. C.
McConnell
, Nature (London)
397
, 338
(1999
).7.
L. J.
Carpenter
, W. T.
Sturges
, S. A.
Penkett
, and P. S.
Liss
, J. Geophys. Res., [Oceans]
104
, 1679
(1999
).8.
B.
Alicke
, K.
Hebstreit
, J.
Stutz
, and U.
Platt
, Nature (London)
397
, 572
(1999
).9.
10.
D. C.
Blomstrom
, K.
Herbig
, and H. E.
Simmons
, J. Org. Chem.
30
, 959
(1965
).11.
12.
P. J.
Kropp
, N. J.
Pienta
, J. A.
Sawyer
, and R. P.
Polniaszek
, Tetrahedron
37
, 3229
(1981
).13.
14.
E. C.
Friedrich
, S. E.
Lunetta
, and E. J.
Lewis
, J. Org. Chem.
54
, 2388
(1989
).15.
S.
Durandetti
, S.
Sibille
, and J.
Pérchon
, J. Org. Chem.
56
, 3255
(1991
).16.
J. M.
Concellón
, P. L.
Bernad
, and J. A.
Pérez-Andrés
, Tetrahedron Lett.
39
, 1409
(1998
).17.
M.
Kawasaki
, S. J.
Lee
, and R.
Bersohn
, J. Chem. Phys.
63
, 809
(1975
).18.
19.
P. M.
Kroger
, P. C.
Demou
, and S. J.
Riley
, J. Chem. Phys.
65
, 1823
(1976
).20.
21.
S. R.
Cain
, R.
Hoffman
, and R.
Grant
, J. Phys. Chem.
85
, 4046
(1981
).22.
23.
L. J.
Butler
, E. J.
Hintsa
, and Y. T.
Lee
, J. Chem. Phys.
84
, 4104
(1986
).24.
L. J.
Butler
, E. J.
Hintsa
, and Y. T.
Lee
, J. Chem. Phys.
86
, 2051
(1987
).25.
E. A. J.
Wannenmacher
, P.
Felder
, and J. R.
Huber
, J. Chem. Phys.
95
, 986
(1991
).26.
G.
Baum
, P.
Felder
, and J. R.
Huber
, J. Chem. Phys.
98
, 1999
(1993
).27.
28.
Q.
Zhang
, U.
Marvet
, and M.
Dantus
, J. Chem. Phys.
109
, 4428
(1998
).29.
K.-W.
Jung
, T. S.
Ahmadi
, and M. A.
El-Sayed
, Bull. Korean Chem. Soc.
18
, 1274
(1997
).30.
W.
Radloff
, P.
Farmanara
, V.
Stert
, E.
Schreiber
, and J. R.
Huber
, Chem. Phys. Lett.
291
, 173
(1998
).31.
32.
S. L.
Baughcum
, H.
Hafmann
, S. R.
Leone
, and D.
Nesbitt
, Faraday Discuss. Chem. Soc.
67
, 306
(1979
).33.
34.
35.
36.
S. Q.
Man
, W. M.
Kwok
, and D. L.
Phillips
, J. Phys. Chem.
99
, 15705
(1995
).37.
38.
39.
S. Q.
Man
, W. M.
Kwok
, A. E.
Johnson
, and D. L.
Phillips
, J. Chem. Phys.
105
, 5842
(1996
).40.
F.
Duschek
, M.
Schmitt
, P.
Vogt
, A.
Materny
, and W.
Kiefer
, J. Raman Spectrosc.
28
, 445
(1997
).41.
M.
Braun
, A.
Materny
, M.
Schmitt
, W.
Kiefer
, and V.
Engel
, Chem. Phys. Lett.
284
, 39
(1998
).42.
43.
44.
45.
46.
G.
Maier
and H. P.
Reisenauer
, Angew. Chem. Int. Ed. Engl.
25
, 819
(1986
).47.
G.
Maier
, H. P.
Reisenauer
, J.
Lu
, L. J.
Scaad
, and B. A.
Hess
, Jr., J. Am. Chem. Soc.
112
, 5117
(1990
).48.
L.
Andrews
, F. T.
Prochaska
, and B. S.
Ault
, J. Am. Chem. Soc.
101
, 9
(1979
).49.
50.
51.
B. J.
Schwartz
, J. C.
King
, J. Z.
Zhang
, and C. B.
Harris
, Chem. Phys. Lett.
203
, 503
(1993
).52.
K.
Saitow
, Y.
Naitoh
, K.
Tominaga
, and Y.
Yoshihara
, Chem. Phys. Lett.
262
, 621
(1996
).53.
A. N.
Tarnovsky
, J.-L.
Alvarez
, A. P.
Yartsev
, V.
Sündstrom
, and E.
Åkesson
, Chem. Phys. Lett.
312
, 121
(1999
).54.
A. N.
Tarnovsky
, M.
Wall
, M.
Rasmusson
, T.
Pascher
, and E.
Åkesson
, J. Chin. Chem. Soc. (Taipei)
47
, 769
(2000
).55.
A. N.
Tarnovsky
, M.
Wall
, M.
Gustafsson
, N.
Lascoux
, V.
Sundström
, and E.
Åkesson
, J. Phys. Chem. A
106
, 5999
(2002
).56.
57.
W. M.
Kwok
, C.
Ma
, A. W.
Parker
, D.
Phillips
, M.
Towrie
, P.
Matousek
, and D. L.
Phillips
, J. Chem. Phys.
113
, 7471
(2000
).58.
59.
60.
X.
Zheng
, W. M.
Kwok
, and D. L.
Phillips
, J. Phys. Chem. A
104
, 10464
(2000
).61.
X.
Zheng
, W.-H.
Fang
, and D. L.
Phillips
, J. Chem. Phys.
113
, 10934
(2000
).62.
X.
Zheng
, C. W.
Lee
, Y.-L.
Li
, W.-H.
Fang
, and D. L.
Phillips
, J. Chem. Phys.
114
, 8347
(2001
).63.
W. M.
Kwok
, C.
Ma
, A. W.
Parker
, D.
Phillips
, M.
Towrie
, P.
Matousek
, X.
Zheng
, and D. L.
Phillips
, J. Chem. Phys.
114
, 7536
(2001
).64.
D. L.
Phillips
, W.-H.
Fang
, and X.
Zheng
, J. Am. Chem. Soc.
123
, 4197
(2001
).65.
D. L.
Phillips
and W.-H.
Fang
, J. Org. Chem.
66
, 5890
(2001
).66.
Y.-L.
Li
, K. H.
Leung
, and D. L.
Phillips
, J. Phys. Chem. A
105
, 10621
(2001
).67.
W.-H.
Fang
, D. L.
Phillips
, D.
Wang
, and Y.-L.
Li
, J. Org. Chem.
67
, 154
(2002
).68.
Y.-L.
Li
, D. M.
Chen
, D.
Wang
, and D. L.
Phillips
, J. Org. Chem.
67
, 4228
(2002
).69.
70.
71.
72.
U.
Bruhlmann
, H.
Buchler
, F.
Marchetti
, and R. E.
Buhler
, Chem. Phys. Lett.
21
, 412
(1973
).73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 98, Revision A.7, Gaussian, Inc., Pittsburgh PA, 1998.
84.
See EPAPS Document No. E-JCPSA6-117–010242 for supporting information on the Cartesian coordinates, total energies and vibrational zero-point energies for selected stationary structures given in Fig. 5.
A direct link to this document may be found in the online article’s HTML reference section. The document may also be reached via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html) or from ftp.aip.org in the directory/epaps/. See the EPAPS homepage for more information.
85.
86.
A. S.
Dneprovskii
, D. V.
Kuznetsov
, E. V.
Eliseenkov
, B.
Fletcher
, and J. M.
Tanko
, J. Org. Chem.
63
, 8860
(1998
).87.
88.
89.
90.
91.
92.
93.
P. S.
Skell
and H. N.
Baxter
III, J. Am. Chem. Soc.
107
, 2823
(1985
).94.
N. J.
Bunce
, K. U.
Ingold
, J. P.
Landers
, J.
Lusztyk
, and J. C.
Scaiano
, J. Am. Chem. Soc.
107
, 5464
(1985
).95.
P. S.
Skell
, H. N.
Baxter
III, J. M.
Tanko
, and V.
Chebolu
, J. Am. Chem. Soc.
108
, 6300
(1986
).96.
N. J.
Bunce
, R. B.
Joy
, J. P.
Landers
, and J. S.
Nakai
, J. Org. Chem.
52
, 1155
(1987
).97.
98.
R.
Breslow
, M.
Brandl
, J.
Hunger
, N.
Turro
, K.
Cassidy
, K.
Krogh-Jespersen
, and J. D.
Westbrook
, J. Am. Chem. Soc.
109
, 7204
(1987
).99.
100.
K. D.
Raner
, J.
Lusztyk
, and K. U.
InGold
, J. Am. Chem. Soc.
110
, 3519
(1988
).101.
J. M.
Tanko
and F. E.
Anderson
III, J. Am. Chem. Soc.
110
, 3525
(1988
).102.
K. D.
Raner
, J.
Lusztyk
, and K. U.
Ingold
, J. Org. Chem.
53
, 5220
(1988
).103.
K. D.
Raner
, J.
Lusztyk
, and K. U.
Ingold
, J. Phys. Chem.
93
, 564
(1989
).104.
K. D.
Raner
, J.
Lusztyk
, and K. U.
Ingold
, J. Am. Chem. Soc.
111
, 3652
(1989
).105.
K. U.
Ingold
, J.
Lusztyk
, and K. D.
Raner
, Acc. Chem. Res.
23
, 219
(1990
).106.
107.
D.
Wang
, Y.-L.
Li
, W. S.
Ho
, K. H.
Leung
, and D. L.
Phillips
, J. Org. Chem.
67
, 747
(2002
).108.
109.
K.-D.
Asmus
, D.
Bahnemann
, C.-H.
Fischer
, and D.
Veltwisch
, J. Am. Chem. Soc.
101
, 5322
(1979
).110.
S. A.
Chaudhri
and K.-D.
Asmus
, Angew. Chem. Int. Ed. Engl.
20
, 672
(1981
).111.
R. L.
Peterson
, D. J.
Nelson
, and M. C. R.
Symons
, J. Chem. Soc., Perkin Trans. 2
1978
, 225
(1978
).112.
M. H.
Champagne
, M. W.
Mullins
, A.
Colson
, and M. D.
Sevilla
, J. Phys. Chem.
95
, 6488
(1991
).113.
L. K.
Steffen
, R. S.
Glass
, M.
Sabahi
, G. S.
Wilson
, C.
Schoneich
, S.
Mahling
, and K.-D.
Asmus
, J. Am. Chem. Soc.
113
, 2141
(1991
).114.
D. K.
Maity
, H.
Mohan
, and J. P.
Mittal
, J. Chem. Soc., Faraday Trans.
90
, 703
(1994
).115.
M. A.
James
, M. L.
McKee
, and A. J.
Illies
, J. Am. Chem. Soc.
118
, 7836
(1996
).116.
M. D.
Sevilla
, S.
Summerfield
, I.
Eliezer
, J.
Rak
, and M. C. R.
Symons
, J. Phys. Chem.
101
, 2910
(1997
).117.
Y.
Gaudel
, L. J.
Marigneir
, and J.
Belloni
, J. Phys. Chem. A
101
, 8979
(1997
).118.
K.-D. Asmus, in Sulfur-Centered Radicals, edited by Z. B. Alfassi (Wiley, New York, 1999), p. 141.
119.
Y.
Gaudel
, H.
Gelabert
, and F.
Guilloud
, J. Am. Chem. Soc.
122
, 5082
(2000
).120.
121.
122.
P. M. W.
Gill
, P.
Weatherall
, and L.
Radom
, J. Am. Chem. Soc.
111
, 2782
(1989
).123.
124.
125.
D. K.
Maity
, H.
Mohan
, and J. P.
Mittal
, J. Phys. Chem.
99
, 12195
(1995
).126.
S. P.
de Visser
, L. J.
de Koning
, and N. M. M.
Nibbering
, J. Phys. Chem.
99
, 15444
(1995
).127.
M. L.
McKee
, A.
Nichols
, and L.
Radom
, J. Am. Chem. Soc.
118
, 10571
(1996
).128.
M.
Aida
, F.
Inoue
, and M.
Kaneko
, J. Am. Chem. Soc.
119
, 12274
(1997
).129.
B.
Braı̈da
, P. C.
Hirberty
, and A.
Savin
, J. Phys. Chem. A
102
, 7872
(1998
).130.
S. P.
de Visser
, L. J.
de Koning
, and N. M. M.
Nibbering
, J. Am. Chem. Soc.
120
, 1517
(1998
).131.
S.
Humbel
, I.
Cote
, N.
Hoffmann
, and J.
Bouquant
, J. Am. Chem. Soc.
121
, 5507
(1999
).132.
133.
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