As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

1.
IUPAC
,
Compendium of Chemical Terminology, The Gold Book
, 2nd ed., edited by
A. D.
McNaught
and
A.
Wilkinson
(
Blackwell Scientific Publications
,
Oxford
,
1997
).
2.
Reactive Intermediate Chemistry
, edited by
R. A.
Moss
,
M. S.
Platz
, and
M.
Jones
(
Wiley-Interscience
,
Hoboken
,
2004
).
3.
G.
Bertrand
,
Carbene Chemistry: From Fleeting Intermediates to Powerful Reagent
(
CRC Press
,
2002
).
4.
R. A.
Moss
and
N. J.
Turro
, in
Kinetics and Spectroscopy of Carbenes and Biradicals
, edited by
M. S.
Platz
(
Plenum
,
New York
,
1990
), pp. 213.
5.
A.
Igau
,
H.
Grützmacher
,
A.
Baceiredo
, and
G.
Bertrand
,
J. Am. Chem. Soc.
110
,
6463
(
1988
).
6.
G.
Bertrand
and
R.
Reed
,
Coord. Chem. Rev.
137
,
323
(
1994
).
7.
A. J.
Arduengo
,
R. L.
Harlow
, and
M.
Kline
,
J. Am. Chem. Soc.
113
,
361
(
1991
).
8.
A. J.
Arduengo
,
F.
Davidson
,
H. V. R.
Dias
,
J. R.
Goerlich
,
D.
Khasnis
,
W. J.
Marshall
, and
T. K.
Prakasha
,
J. Am. Chem. Soc.
119
,
12742
(
1997
).
9.
N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools
, edited by
S.
Diez-González
(
RSC Catalysis Series
,
U.K.
,
2010
).
10.
E.
Aldeco-Perez
,
A. J.
Rosenthal
,
B.
Donnadieu
,
P.
Parameswaran
,
G.
Frenking
, and
G.
Bertrand
,
Science
326
,
556
(
2009
).
11.
K.
Hirai
,
T.
Itoh
, and
H.
Tomioka
,
Chem. Rev.
109
,
3275
(
2009
).
12.
R.
Moss
,
A. L.
Wang
,
C. M.
Odorisio
,
M.
Zhang
, and
K.
Krogh-Jespersen
,
J. Phys. Chem. A
114
,
209
(
2010
).
13.
C.
Gonzalez
,
A.
Restrepo-Cossio
,
M.
Márquez
,
K. B.
Wiberg
, and
M.
De Rosa
,
J. Phys. Chem. A
102
,
2732
(
1998
).
14.
Y.
Zhang
, Ph.D. thesis,
The Ohio State University, EEUU
,
2010
.
15.
I. R.
Gould
,
N. J.
Turro
,
J.
Butcher
,
C.
Doubleday
,
N. P.
Hacker
,
G. F.
Lehr
,
R. A.
Moss
,
D. P.
Cox
, and
W.
Guo
,
Tetrahedron
41
,
1587
(
1985
).
16.
N. J.
Turro
,
J. A.
Butcher
,
R. A.
Moss
,
W.
Guo
,
R. C.
Munjal
, and
M.
Fedorynski
,
J. Am. Chem. Soc.
102
,
7576
(
1980
).
17.
J.
Peon
,
D.
Polshakov
, and
B.
Kohler
,
J. Am. Chem. Soc.
124
,
6428
(
2002
).
18.
J.
Wang
,
J.
Kubicki
,
E. F.
Hilinski
,
S. L.
Mecklenburg
,
T. L.
Gustafson
, and
M. S.
Platz
,
J. Am. Chem. Soc.
129
,
13683
(
2007
).
19.
J.
Wang
,
G.
Burdzinski
,
T. L.
Gustafson
, and
M. S.
Platz
,
J. Org. Chem.
71
,
6221
(
2006
).
20.
J.
Wang
,
G.
Burdzinski
,
T. L.
Gustafson
, and
M. S.
Platz
,
J. Am. Chem. Soc.
129
,
2597
(
2007
).
21.
R. A.
Moss
,
J. Org. Chem.
75
,
5773
(
2010
).
22.
R. A.
Moss
,
J.
Tian
,
R. R.
Sauers
, and
K.
Krogh-Jespersen
,
J. Am. Chem. Soc.
129
,
10019
(
2007
).
23.
R. A.
Moss
,
J. Phys. Org. Chem.
24
,
866
(
2011
).
24.
E. M.
Tippmann
,
M. S.
Platz
,
I. B.
Svir
, and
O. V.
Klymenko
,
J. Am. Chem. Soc.
126
,
5750
(
2004
).
25.
R. A.
Moss
,
L.
Wang
,
E.
Weintraub
, and
K.
Krogh-Jespersen
,
J. Phys. Chem. A
112
,
4651
(
2008
).
26.
R. A.
Moss
,
L.
Wang
,
C. M.
Odorisio
, and
K.
Krogh-Jespersen
,
Tetrahedron Lett.
51
,
1467
(
2010
).
27.
P. A.
Hoijemberg
,
R. A.
Moss
, and
K.
Krogh-Jespersen
,
J. Phys. Chem. A
116
,
358
(
2012
).
28.
J.
Wang
,
J.
Kubicki
,
T. L.
Gustafson
, and
M. S.
Platz
,
J. Am. Chem. Soc.
130
,
2304
(
2008
).
29.
J. F.
Pérez
and
A.
Restrepo
,
ASCEC V-02: Annealing Simulado Con Energía Cuántica
(
Universidad de Antioquia
,
Medellín, Colombia
,
2008
).
30.
J. F.
Pérez
,
C. Z.
Hadad
, and
A.
Restrepo
,
Int. J. Quantum Chem.
108
,
1653
(
2008
).
31.
J. F.
Perez
,
E.
Florez
,
C. Z.
Hadad
,
P.
Fuentealba
, and
A.
Restrepo
,
J. Phys. Chem. A
112
,
5749
(
2008
).
32.
D.
Yepes
,
S.
Kirk
,
S.
Jenkins
, and
A.
Restrepo
,
J. Mol. Model.
18
,
4171
(
2012
).
33.
J.
David
,
D.
Guerra
,
C. Z.
Hadad
, and
A.
Restrepo
,
J. Phys. Chem. A
114
,
10726
(
2010
).
34.
J.
David
,
D.
Guerra
, and
A.
Restrepo
,
Chem. Phys. Lett.
64
,
539
-
540
(
2012
).
35.
J.
Murillo
,
J.
David
, and
A.
Restrepo
,
Phys. Chem. Chem. Phys.
12
,
10963
(
2010
).
36.
S.
Gomez
,
D.
Guerra
,
J.
David
, and
A.
Restrepo
,
J. Mol. Model.
19
,
2173
(
2013
).
37.
J.
David
,
D.
Guerra
, and
A.
Restrepo
,
J. Phys. Chem. A
113
,
10167
(
2009
).
38.
F.
Ramírez
,
C. Z.
Hadad
,
D.
Guerra
,
J.
David
, and
A.
Restrepo
,
Chem. Phys. Lett.
507
,
229
(
2011
).
39.
G.
Hincapié
,
N.
Acelas
,
M.
Castano
,
J.
David
, and
A.
Restrepo
,
J. Phys. Chem. A
114
,
7809
(
2010
).
40.
S.
Jenkins
,
A.
Restrepo
,
J.
David
,
D.
Yin
, and
S.
Kirk
,
Phys. Chem. Chem. Phys.
13
,
11644
(
2011
).
41.
C.
Ibargüen
,
M.
Manrique–Moreno
,
C. Z.
Hadad
,
J.
David
, and
A.
Restrepo
,
Phys. Chem. Chem. Phys.
15
,
3203
(
2013
).
42.
J.
Gonzalez
,
E.
Florez
,
J.
Romero
,
A.
Reyes
, and
A.
Restrepo
,
J. Mol. Model.
19
,
1763
(
2013
).
43.
J.
Romero
,
A.
Reyes
,
J.
David
, and
A.
Restrepo
,
Phys. Chem. Chem. Phys.
13
,
15264
(
2011
).
44.
R.
Bader
,
Atoms in Molecules: A Quantum Theory
(
Oxford University Press
,
USA
,
1994
).
45.
E. D.
Glendening
,
C. R.
Landis
, and
F.
Weinhold
,
Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
,
1
(
2012
).
46.
S.
Grimme
,
J. Comput. Chem.
27
,
1787
(
2006
).
47.
R. A.
Moss
,
L.
Wang
,
C. M.
Odorisio
, and
K.
Krogh-Jespersen
,
J. Am. Chem. Soc.
132
,
10677
(
2010
).
48.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
,
G. E.
Scuseria
,
M. A.
Robb
,
J. R.
Cheeseman
,
G.
Scalmani
,
V.
Barone
,
B.
Mennucci
,
G. A.
Petersson
,
H.
Nakatsuji
,
M.
Caricato
,
X.
Li
,
H. P.
Hratchian
,
A. F.
Izmaylov
,
J.
Bloino
,
G.
Zheng
,
J. L.
Sonnenberg
,
M.
Hada
,
M.
Ehara
,
K.
Toyota
,
R.
Fukuda
,
J.
Hasegawa
,
M.
Ishida
,
T.
Nakajima
,
Y.
Honda
,
O.
Kitao
,
H.
Nakai
,
T.
Vreven
,
J. A.
Montgomery
, Jr.
,
J. E.
Peralta
,
F.
Ogliaro
,
M.
Bearpark
,
J. J.
Heyd
,
E.
Brothers
,
K. N.
Kudin
,
V. N.
Staroverov
,
R.
Kobayashi
,
J.
Normand
,
K.
Raghavachari
,
A.
Rendell
,
J. C.
Burant
,
S. S.
Iyengar
,
J.
Tomasi
,
M.
Cossi
,
N.
Rega
,
J. M.
Millam
,
M.
Klene
,
J. E.
Knox
,
J. B.
Cross
,
V.
Bakken
,
C.
Adamo
,
J.
Jaramillo
,
R.
Gomperts
,
R. E.
Stratmann
,
O.
Yazyev
,
A. J.
Austin
,
R.
Cammi
,
C.
Pomelli
,
J. W.
Ochterski
,
R. L.
Martin
,
K.
Morokuma
,
V. G.
Zakrzewski
,
G. A.
Voth
,
P.
Salvador
,
J. J.
Dannenberg
,
S.
Dapprich
,
A. D.
Daniels
,
O.
Farkas
,
J. B.
Foresman
,
J. V.
Ortiz
,
J.
Cioslowski
,
D. J.
Fox
 et al,
Gaussian 09
, Revision A.01,
Gaussian, Inc.
,
Wallingford, CT
,
2009
.
49.
T. A.
Keith
, AIMAll version 10.09.12, TK Gristmill Software, Overland Park KS, USA, 2010, http://aim.tkgristmill.com.
50.
E. D.
Glendening
,
A. E.
Reed
,
J. E.
Carpenter
, and
F.
Weinhold
, NBO Version 3.1., Theoretical Chemistry Institute, University of Wisconsin, Madison, 1998.
51.
C. Z.
Hadad
,
A.
Restrepo
,
S.
Jenkins
,
F.
Ramírez
, and
J.
David
,
Theor. Chem. Acc.
132
,
1376
(
2013
).
52.
S.
Grabowski
,
Chem. Rev.
111
,
2597
(
2011
).
53.
S.
Jenkins
and
I.
Morrison
,
Chem. Phys. Lett.
317
,
97
(
2000
).
54.
B.
Yan
,
S.
Jaeqx
,
W. J.
van der Zande
, and
A. M.
Rijs
,
Phys. Chem. Chem. Phys.
16
,
10770
(
2014
).
55.
See supplementary material at http://dx.doi.org/10.1063/1.4913568 for accessing appendices A1, A2, A3, and A4 which complement arguments and results of the article.

Supplementary Material

You do not currently have access to this content.