Palladium-catalyzed selective fluorination of o-carboranes

Article abstract of DOI:10.1021/ja405808t

A Pd(II)-catalyzed direct selective fluorination reaction of carboranes using a F⁺ reagent has been developed, leading to a series of polyfluorocarboranes in high isolated yields. The mechanism involving electrophilic B-H activation, oxidation of Pd(II) by F⁺ species, and reductive elimination is proposed.

Full text of DOI:10.1021/ja405808t

Subscriber access provided by Otterbein University
Communication
Palladium-Catalyzed Selective Fluorination of o-Carboranes
Zaozao Qiu, Yangjian Quan, and Zuowei Xie
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja405808t • Publication Date (Web): 09 Aug 2013
Downloaded from http://pubs.acs.org on August 12, 2013
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Palladium-Catalyzed Selective Fluorination of o-Carboranes
Zaozao Qiu,† Yangjian Quan,‡ and Zuowei Xie*,†,‡
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
† Shanghai‐Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
‡ Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong
Kong, Shatin, New Territories, Hong Kong, China
Supporting Information Placeholder
tution reaction between arenes and carboranes,5a,15 we initi‐
ABSTRACT: Palladium(II)‐catalyzed direct selective fluori‐
nation reaction of carboranes using F+ reagent has been de‐
ated a research program to develop transition metal cata‐
lyzed direct fluorination of carboranes, and report herein a
regioselective, efficient and safe method for the preparation
of polyfluorocarboranes via Pd(II)‐catalyzed B–H activation
(Scheme 1).
veloped, leading to a series of polyfluorocarboranes in high
isolated yields. The mechanism involving electrophilic B–H
activation, oxidation of Pd(II) by F+ species and reductive
elimination is proposed.
Scheme 1. Fluorination of o‐Carboranes
Functionalization of carboranes has received a growing in‐
terest owing to their applications in medicine as boron neu‐
tron capture therapy (BNCT) agents,1 in supramolecular de‐
sign as building blocks,2 and in coordination/organometallic
chemistry as ligands.3 Since the substitution of hydrogen for
fluorine can significantly change both physical and chemical
properties of compounds,4 it is anticipated that polyfluori‐
nated carboranes would have great potential as key compo‐
nents of n‐type organic semiconductors and donor‐acceptor
type of materials owing to their super electron‐deficient na‐
ture,5a‐d of new BNCT agents due to enhanced biostability,4
and of weakly coordinating anions because of improved
chemical inertness.5e In general, there are two conventional
synthetic methods leading to the cage boron substituted
carboranes: electrophilic substitution at cage BH vertices by
o‐Carborane B–H activation by low‐valent transition met‐
als via oxidative addition has been known,16,17 which requires
a directing group and has been a stoichmetric process.18,19 In
view of the unique electronic structure of carboranes, we
selected electrophilic transition metal species as catalysts
and F+ reagents as fluorination sources since the charge dis‐
tribution of the cage20 could make a selective fluorination
feasible in the absence of a directing group. The screening
results were summarized in Table 1.
2‐
electrophiles6 and capitation reaction of nido‐C2B9H11 with
boron halides.7 Direct electrophilic halogenation is known to
be an effective and convenient method for the preparation of
cage boron chlorinated, brominated and iodinated carbo‐
ranes.8 Selective mono‐, di‐, or polyhalogenation of carbo‐
ranes can be achieved under appropriate conditions. In con‐
trast, reaction of carborane with elemental fluorine is not
selective, resulting in the formation of deca‐B‐
fluorocarborane C2B10H2F10.9 Though nucleophilic substitu‐
tion reaction of carboranyl diazonium,10 thallium11 or io‐
donium12 salts with F‐ affords the corresponding mono‐B‐
fluorocarboranes, the only reported selective fluorination of
carboranes is to use SbF5 as reagent. Such reactions must be
performed in special perfluorinated hydrocarbon solvents
under precisely controlled conditions in order to achieve the
selectivity.13 Such reactions also involve the formation of HF,
which largely limits the use of this method (Scheme 1).
Most of the Pd(II) complexes were catalytically active with
Pd(MeCN)4(BF4)2 giving 8,9,10,12‐tetrafluorinated product 2a
in the best selectivity of 33% among mixtures of geometrical
isomers of the tetrafluorinated species (Table 1, entries 4–8).
In sharp contrast, nickel and platinum complexes such as
NiCl2(PPh3)2 and PtCl2(PPh3)2 were inactive (Table 1, entries 2
and 3). In the absence of a catalyst, no reaction was observed
between 1a and F+ reagents (Table 1, entry 1). The yield and
selectivity remained almost unchanged if the catalyst loading
was increased from 0.5 to 1 equiv (0.5 equiv represents 12.5
mol% of catalyst loading per B‐H conversion; Table 1, entry
9). The use of F+2 led to a higher ratio of tetrafluorocarbo‐
ranes as mixtures of geometrical isomers but the selectivity
for 2a had no obvious changes (Table 1, entry 10). F+3 resulted
in the formation of mixtures of geometrical isomers of penta‐
fluorocarboranes as major products (Table 1, entry 11). On the
Inspired by transition metal catalyzed direct fluorination
of aryl C–H bonds,14 and the similarity in electrophilic substi‐
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
Table 1. Fluorination of o‐Carboranes with F+ Reagents Catalyzed by Transition Metal Complexesa
1
2
3
4
5
6
catalyst
F+
F
R
R
R
R
R
R
O
S
O
S
F
F
Fn
Ph
N
Ph
F
MeCN
110 oC, 2d
N
N
N
F
-
-
F
F
OTf-
F+1
F
O
O
BF4
F+3
BF4
F+2
2a R = H
2b R = Me
F+4
1a R = H
1b R = Me
product (%)[b]
F3 F4(2)
7
8
9
entry
1
catalyst
F+
F1
F2
F5
1
2
1a or 1b
1a
none
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+1
10 eq. F+2
10 eq. F+3
10 eq. F+4
10 eq. F+1
5 eq. F+1
10 eq. F+1
5 eq. F+1
N.R.
N.R.
N.R.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
0.5 eq. NiCl2(PPh3)2
0.5 eq. PtCl2(PPh3)2
0.5 eq. PdCl2(PPh3)2
0.5 eq. Pd(OAc)2
0.5 eq. Pd(TFA)2
3
1a
4
1a
messy
21
5
1a
‐
12
‐
‐
60
‐
89(13)
1(1)
‐
‐
6
1a
27
‐
7
1a
0.5 eq. Pd(MeCN)4(OTf)2
0.5 eq. Pd(MeCN)4(BF4)2
1 eq. Pd(MeCN)4(BF4)2
1 eq. Pd(MeCN)4(BF4)2
1 eq. Pd(MeCN)4(BF4)2
1 eq. Pd(MeCN)4(BF4)2
0.2 eq. Pd(MeCN)4(BF4)2
1 eq. Pd(MeCN)4(BF4)2
0.5 eq. Pd(MeCN)4(BF4)2
0.5 eq. Pd(MeCN)4(BF4)2
55(31)
61(33)
67(36)
94(37)
11(‐)
45
39
33
‐
8
1a
‐
‐
‐
9
1a
‐
‐
‐
10
11
12
13
14
15
16
1a
‐
‐
6
1a
‐
‐
‐
89
‐
1a
‐
5
2
27
‐
63
35
50
‐
32(20)
63(21)
23(6)
1a
‐
‐
1a
‐
‐
1b
1b
‐
87(87)
86(86)
10
11
‐
‐
‐
aReactions were conducted at 0.02 mmol scale in 0.5 mL of CH3CN at 110 oC for 2 d. bThe ratio and selectivity of 2 were determined
by GC‐MS. Noted that there were several geometrical isomers of tetrafluorinated species.
Table 2. Solvent and Additive Effects on Pd(II)‐Catalyzed Fluorination of o‐Carboranea
product (%)b
entry
solvent
T (oC)
additive
F0
48
87
100
‐
F1
46
13
‐
F2
‐
F3
‐
F4(2a)
F5
‐
1
THF
toluene
PhCF3
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
110
110
110
110
80
50
‐
‐
2
3
4
5
6
7
8
9
‐
‐
‐
‐
‐
‐
‐
‐
‐
‐
‐
‐
‐
‐
61(33)
39
19
‐
‐
‐
‐
‐
59
26
26
‐
22(9)
‐
‐
4
70
‐
‐
110
110
110
2 eq. PPh3
2 eq. NEt3
1 eq. BiPy
‐
‐
73(19)
1
66
34
‐
‐
‐
58
42
‐
‐
‐
‐
aReactions were conducted at 0.02 mmol scale in 0.5 mL of solvents. bThe ratio and 2a selectivity were determined by GC‐MS.
other hand, F+4 was the least reactive, giving a mixture of di‐,
tri‐ and tetrafluorinated carboranes. In view of efficiency, 2a
selectivity and easy separation of 2a, entry 8 (Table 1) was
selected as the optimal reaction condition.
2
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
For 1,2‐dimethyl‐o‐carborane 1b, both the yields and selec‐
Scheme 2. Fluorination of B‐Methyl‐o‐carboranes
1
2
3
4
5
6
7
8
tivities were substantially increased. Compound 2b was ob‐
tained as the only tetrafluorinated isomer. This result can be
attributed to the increased charge gap among cage boron
atoms imposed by the methyl groups on cage carbons (Table
1, entries 15–16).21
Me
Me
F
Me
Me
Me
Me
F
F
F
Me
Me
2o, 93%
3p, 53%
1o
1p
We then investigated the effects of solvents, temperatures
and additives on this reaction. The results were compiled in
Table 2. As Pd(MeCN)4(BF4)2 catalyst was very poorly soluble
in THF, toluene and trifluoromethylbenzene, the fluorina‐
tion efficiency was very low (Table 2, entries 1–3). Tempera‐
tures below 110 oC resulted in the decreased amount of tetra‐
fluorocarboranes (Table 2, entries 4–6). Addition of PPh3 led
to a big drop in both 2a selectivity and pentafluorinated
products, whereas NEt3 and bipyridine (Bipy) significantly
lowered the reactivity (Table 2, entries 7–9).
Me
Me
Me
Me
Me
Me
0.5 eq. Pd(MeCN)4(BF4)2
F
F
F
9
10 eq.
N
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
OTf-
F
MeCN, 110 o
C
Me
Me
Me
Me
Me
Me
Me
F
F
Me
1q
4q, 88%
substituents, were not compatible with this reaction, produc‐
ing mixtures of polyfluorocarboranes. On the other hand,
under similar reaction conditions, 13‐ and 14‐vertex carbo‐
ranes22 gave the cage degradation products, finally leading to
BF3 as evidenced by 11B NMR spectra.
Compounds 2–4 were fully characterized by 1H, 13C, 11B and
19F NMR spectroscopic data as well as high‐resolution mass
spectrometry. The molecular structures of 2b, g, k, l, m, 3p
and 4q were further confirmed by single‐crystal X‐ray analy‐
ses (see Figures S1‐S7 in SI)
The reaction scope of this Pd(II)‐catalyzed fluorination
process was examined using various carboranes under opti‐
mal reaction conditions. The results were summarized in
Table 3. Except that o‐carborane 1a offered the low isolated
yield (31%) of the desired 8,9,10,12‐tetrafluorocarborane 2a,
excellent regioselectivities were observed for mono‐ and di‐
C‐substituted‐o‐carboranes,
affording
tetrafluorination
products 2b–n in very good isolated yields (64~91%). In addi‐
tion, 1,2,4,7‐tetramethyl‐o‐carborane 1o gave 1,2,4,7‐
tetramethyl‐8,9,10,12‐tetrafluoro‐o‐carborane 2o in 93% iso‐
lated yield. 1,2,12‐Trimethyl‐o‐carborane 1p and 1,2,9,12‐
tetramethyl‐o‐carborane 1q produced the corresponding tri‐
and difluoro‐o‐carboranes [1,2,12‐trimethyl‐8,9,10‐trifluoro‐o‐
carborane (3p) and 1,2,9,12‐tetramethyl‐8,10‐difluoro‐o‐
carborane (4q)] in 53% and 88% isolated yields, respectively
(Scheme 2). Phenyl and alkenyl groups were tolerated with
this reaction condition. It was noteworthy that carboranes
with Lewis‐base functionalities, such as N, O or S containing
A palladium(II)‐catalyzed fluorination process is proposed
as the plausible mechanism. The electrophilic palladation of
cage B–H is favored at the most nucleophilic site of o‐
carborane.20 The strong oxidant F+ reagent can oxidatively
add to the Pd(II) species to give a Pd(IV) complex,14,23 which
undergoes reductive elimination to generate the B–F bond
and reproduce the Pd(II). It is noted that the reductive elim‐
ination from a high‐valent palladium fluoride species would
‐
be facilitated by a noncoordinating counterion BF4 and
Table 3. Pd(II)‐Catalyzed Regioselective Tetrafluori‐
nation of o‐Carboranesa,b
weakly donating ligand CH3CN.
In summary, a regioselective, efficient and safe palla‐
dium(II)‐catalyzed direct fluorination of carboranes through
B–H activation was developed, in which F+ species func‐
tioned as a fluorinating reagent as well as oxidant. This
serves as a new methodology for the generation of a series of
polyfluorocarboranes, which does not require special sol‐
vents and reaction vessels. This work also sets an example of
catalytic electrophilic substitution of cage B‐H bonds.
ASSOCIATED CONTENT
Supporting Information
Ph
F
F
Ph
F
F
F
F
F
F
H
Experimental details, complete characterization data, and X‐
ray crystallographic data. This material is available free of
charge via the Internet at http://pubs.acs.org.
2h,d 83%
2f,d 74%
AUTHOR INFORMATION
Corresponding Author
zxie@cuhk.edu.hk
Notes
The authors declare no competing financial interests.
b
aIsolated yields. Reactions were conducted at 0.2 mmol scale
ACKNOWLEDGMENT
in 5 mL of CH3CN at 110 oC. cHeated for 4 d. dHeated for 2 d.
3
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
(13) Lebedev, V. N.; Balagurova, E. V.; Polyakov, A. V.; Yanovsky, A.
I.; Struchkov, Yu. T.; Zakharkin, L. I. J. Organomet. Chem. 1990, 385,
307.
(14) (a) Hull, K. L.; Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc.
2006, 128, 7134. (b) Wang, X.; Mei, T. S.; Yu, J.‐Q. J. Am. Chem. Soc.
2009, 131, 7520. (c) Wu, T.; Yin, G.; Liu, G. J. Am. Chem. Soc. 2009, 131,
16354. (d) Chan, K. S. L.; Wasa, M.; Wang, X.; Yu, J.‐Q. Angew. Chem.
Int. Ed. 2011, 50, 9081.
This work was supported by grants from National Basic Re‐
search Program of China (973 Program, Grant No.
2012CB821600), and the Research Grants Council of The
Hong Kong Special Administration Region (Project Nos.
CUHK7/CRF/12G and 403912). Dedicated to Professor Guo-
Qiang Lin on the occasion of his 70th birthday.
1
2
3
4
5
6
7
8
(15) King, R. B. Chem. Rev. 2001, 101, 1119.
REFERENCES
(16) Selected examples: (a) Hoel, E. L.; Hawthorne, M. F. J. Am.
Chem. Soc. 1975, 97, 6388. (b) Farràs, P.; Olid‐Britos, D.; Viñas, C.;
Teixidor, F. Eur. J. Inorg. Chem. 2011, 2525. (c) D’yachihin, D. I.; Dol‐
gushin, F. M.; Godovikov, I. A.; Chizhevsky, I. T. J. Organomet.
Chem. 2011, 696, 3846. (d) Liu, D.; Dang, L.; Sun, Y.; Chan, H.‐S.; Lin,
Z.; Xie, Z. J. Am. Chem. Soc. 2008, 130, 16103. (e) Herberhold, M.; Yan,
H.; Milius, W.; Wrackmeyer, B. Angew. Chem. Int. Ed. 1999, 38, 3689.
(f) Liu, G.; Hu, J.; Wen, J.; Dai, H.; Li, Y.; Yan, H. Inorg. Chem. 2011,
50, 4187. (g) Zhang, R.; Zhu, L.; Liu, G.; Dai, H.; Lu, Z.; Zhao, J.; Yan,
H. J. Am. Chem. Soc. 2012, 134, 10341. (h) Jin, G.‐X.; Wang, J.‐Q.;
Zhang, C.; Weng, L.‐H.; Herberhold, M. Angew. Chem. Int. Ed. 2004,
44, 259. (i) Yao, Z.‐J.; Su, G.; Jin, G.‐X. Chem. Eur. J. 2011, 17, 13298.
(17) For transition metal promoted hydroboration of carborane
anions, see: (a) Hewes, J. D.; Kreimendahl, C. W.; Marder, T. B.;
Hawthorne, M. F. J. Am. Chem. Soc. 1984, 106, 5757. (b) Teixidor, F.;
Casabó, J.; Romerosa, A. M.; Viñas, C.; Rius, J.; Miravitlles, C. J. Am.
Chem. Soc. 1991, 113, 9895. (c) Du, S. W.; Kautz, J. A.; McGrath, T. D.;
Stone, F. G. A. Chem. Commun. 2002, 1004. (d) Rojo, I.; Teixidor, F.;
Kivekäs, R.; Sillanpää, R.; Viñas, C. J. Am. Chem. Soc. 2003, 125, 14720.
(e) Molinos, E.; Brayshaw, S. K.; Kociok‐Köhn, G.; Weller, A. S. Or‐
ganometallics 2007, 26, 2370. (f) Chatterjee, S.; Carroll, P. J.; Sned‐
don, L. G. Inorg. Chem. 2010, 49, 3095.
(18) (a) Spokoyny, A. M.; Reuter, M. G.; Stern, C. L.; Ratner, M. A.;
Seideman, T.; Mirkin, C. A. J. Am. Chem. Soc. 2009, 131, 9482. (b) El‐
Zaria, M. E.; Arii, H.; Nakamura, H. Inorg. Chem. 2011, 50, 4149. (c)
Prokhorov, A. M.; Slepukhin, P. A.; Rusinov, V. L.; Kalininc, V. N.;
Kozhevnikovab, D. N. Chem. Commun. 2011, 47, 7713. (d) Fey, N.;
Haddow, M. F.; Mistry, R.; Norman, N. C.; Orpen, A. G.; Reynolds, T.
J.; Pringle, P. G. Organometallics 2012, 31, 2907.
(19) The only example of metal‐catalyzed hydroboration of termi‐
nal alkyne with o‐C2B10H12, see: Mirabelli, M. G. L.; Sneddon, L. G. J.
Am. Chem. Soc. 1988, 110, 449.
(20) (a) Potenza, J. A.; Lipscomb, W. N.; Vickers, G. D.; Schroeder,
H. A. J. Am. Chem. Soc. 1966, 88, 628. (b) Hoffmann, R.; Lipscomb,
W. N. J. Chem. Phys. 1962, 36, 2179. (c) Koetzle, T. F.; Lipscomb, W.
N. Inorg. Chem. 1970, 9, 2743. (d) Dixon, D. A.; Kleier, D. A.; Helgren,
T. A.; Hall, J. H.; Lipscomb, W. N. J. Am. Chem. Soc. 1977, 99, 6226.
(21) Teixidor, F.; Barberà, G.; Vaca, A.; Kivekäs, R.; Sillanpää, R.;
Oliva, J.; Viñas, C. J. Am. Chem. Soc. 2005, 127, 10158.
(22) (a) Deng, L.; Chan, H.‐S.; Xie, Z. Angew. Chem. Int. Ed. 2005,
44, 2128. (b) Deng, L.; Chan, H.‐S.; Xie, Z. J. Am. Chem.
Soc. 2006, 128, 5219. (c) Deng, L.; Zhang, J.; Chan, H.‐S.; Xie, Z. An‐
gew. Chem. Int. Ed. 2006, 45, 4309. (d) Zhang, J.; Deng, L.; Chan, H.‐
S.; Xie, Z. J. Am. Chem. Soc. 2007, 129, 18. (e) Deng, L.; Xie, Z. Or‐
ganometallics 2007, 26, 1832. (f) Zhang, J.; Xie, Z. Chem. Asian J. 2010,
5, 1742.
(23) (a) Dick, A. R.; Kampf, J. W.; Sanford, M. S. J. Am. Chem. Soc.
2005, 127, 12790. (b) Furuya, T.; Ritter, T. J. Am. Chem. Soc. 2008, 130,
10060. (c) Kaspi, A. W.; Yahav‐Levi, A.; Goldberg, I.; Vigalok, A.
Inorg. Chem. 2008, 47, 5. (d) Ball, N. D.; Sanford, M. S. J. Am. Chem.
Soc. 2009, 131, 3796. (e) Qiu, S.; Xu, T.; Zhou, J.; Guo, Y.; Liu, G. J.
Am. Chem. Soc. 2010, 132, 2856. (f) Powers, D. C.; Ritter, T. Nature
chem. 2009, 1, 302. (g) Engle, K. M.; Mei, T.‐S.; Wang, X.; Yu, J.‐Q.
Angew. Chem. Int. Ed. 2011, 50, 1478. (h) McMurtrey, K. B.; Racowski,
J. M.; Sanford. M. S. Org. Lett. 2012, 14, 4094.
(1) (a) Hawthorne, M. F. Angew. Chem. Int. Ed. 1993, 32, 950. (b)
Armstrong, A. F.; Valliant, J. F. Dalton Trans. 2007, 4240. (c) Issa, F.;
Kassiou, M.; Rendina, L. M. Chem. Rev. 2011, 111, 5701.
(2) Selected examples: (a) Yang, X.; Jiang, W.; Knobler, C. B.
Hawthorne, M. F. J. Am. Chem. Soc. 1992, 114, 9719. (b) Jude, H.;
Disteldorf, H.; Fischer, S.; Wedge, T.; Hawkridge, A. M.; Arif, A. M.;
Hawthorne, M. F.; Muddiman, D. C.; Stang, P. J. J. Am. Chem. Soc.
2005, 127, 12131. (c) Dash, B. P.; Satapathy, R.; Gaillard, E. R.; Maguire,
J. A.; Hosmane; N. S. J. Am. Chem. Soc., 2010, 132, 6578.
(3) (a) Hosmane, N. S.; Maguire, J. A. In Comprehensive Or‐
ganometallic Chemistry III.; Crabtree R. H.; Mingos, D. M. P. Eds.;
Elsevier: Oxford, 2007; Vol. 3, Chapter 5. (b) Xie Z. Coord. Chem. Rev.
2002, 231, 23. (c) Xie, Z. Acc. Chem. Res. 2003, 36, 1. (d) Deng, L.; Xie,
Z. Coord. Chem. Rev. 2007, 251, 2452.
(4) (a) Banks, R. E.; Smart, B. E.; Tatlow, J. C., Eds. Organofluorine
Chemistry: Principles and Commercial Applications; Plenum Press:
New York, 1994. (b)Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed.
2005, 44, 214. (c) Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317,
1881.
(5) (a) Grimes, R. M. Carboranes, 2nd ed.; Academic Press: Am‐
sterdam, 2011. (b) Lyssenko, K. A.; Antipin, M. Yu.; Lebedev, V. N.
Inorg. Chem. 1998, 37, 5834. (c) Nicoud, J.‐F.; Bolze, F.; Sun, X.‐H.;
Hayek, A.; Baldeck, P. Inorg. Chem. 2011, 50, 4272. (d) Hosmane, N. S.
Boron Science: New Technologies and Applications; CRC Press: Boca
Raton, FL, USA, 2011. (e) Reed, C. A. Acc. Chem. Res. 1998, 31, 133.
(6) Selected examples: (a) Zheng, Z.; Jiang, W.; Zinn, A. A.; Kno‐
bler, C. B.; Hawthorne, M. F. Inorg. Chem. 1995, 34, 2095. (b) Bar‐
berà, G.; Viñas, C.; Teixidor, F.; Sillanpää, R.; Kivekäs, R. Inorg. Chem.
2006, 45, 3496. (c)Dash, B. P.; Satapathy, R.; Maguire, J. A.; Hos‐
mane, N. S. Org. Lett. 2008, 10, 2247. (d) Puga, A. V.; Teixidor, F.;
Sillanpää, R.; Kivekäs, R.; Viñas, C. Chem. Eur. J. 2009, 15, 9764. (e)
Spokoyny, A. M.; Machan, C. W.; Clingerman, D. J.; Rosen, M. S.;
Wiester, M. J.; Kennedy, R. D.; Stern, C. L.; Sarjeant, A. A.; Mirkin, C.
A. Nature Chem. 2011, 3, 590.
(7) Selected examples: (a) Viñas, C.; Barberà, G.; Oliva, J. M.; Teix‐
idor, F.; Welch, A. J.; Rosair, G. M. Inorg. Chem. 2001, 40, 6555. (b)
Barberà, G.; Teixidor, F.; Viñas, C.; Sillanpää, R.; Kivekäs, R. Eur. J.
Inorg. Chem. 2003, 1511. (c) Ogawa, T.; Ohta, K.; Yoshimi, T.; Yama‐
zaki, H.; Suzuki, T.; Ohta, S.; Endo, Y. Bioorg. Med. Chem. Lett. 2006,
16, 3943. (d) Safronov, A. V.; Shlyakhtina, N. I.; Hawthorne, M. F.
Organometallics 2012, 31, 2764.
(8) Selected examples: (a) Schroeder, H.; Heying, T. L.; Reiner, J.
R. Inorg. Chem., 1963, 2, 1092. (b) Smith, H. D.; Knowles, T. A.;
Schroederz, H. Inorg. Chem., 1965, 4, 107. (c) Andrews, J. S.; Zayas, J.
Jones, M., Jr. Inorg. Chem. 1985, 24, 3715. (d) Jiang, W.; Knobler, C. B.;
Curtis, C. E.; Mortimer, M. D.; Hawthorne, M. F. Inorg. Chem. 1995,
36, 3491. (e) Srivastava, R. R.; Hamlin, D. K.; Wilbur, D. S. J. Org.
Chem. 1996, 61, 9041. (f) Barberà, G.; Vaca, A.; Teixidor, F.; Sillanpää,
R.; Kivekäs, R.; Viñas, C. Inorg. Chem. 2008, 47, 7309. (g) Eriksson, L.;
Winberg, K. J.; Claro, R. T.; Sjöberg, S. J. Org. Chem. 2003, 68, 3569.
(h) Himmelspach, A.; Finze, M. Eur. J. Inorg. Chem. 2010, 2012.
(9) Kongpricha, S.; Schroeder, H. Inorg. Chem. 1969, 8, 2449.
(10) (a) Zakharkin, L. I.; Kalinin, V. N.; Kvasov, B. A.; Fedin, E. I.
Izv. Akad. Nauk SSSR, Ser. Khim. 1968, 2415. (b) Zakharkin, L. I.;
Kalinin, V. N.; Gedymin, V. V. J. Organomet. Chem. 1969, 16, 371.
(11) Bregadze, V. I.; Usyatinsky, A. Ya.; Godovikov, N. N. Izv. Akad.
Nauk SSSR, Ser. Khim. 1979, 2836.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(12) (a) Grushin, V. V.; Shcherbina, T. M.; Tolstaya, T. P. J. Or‐
ganomet. Chem. 1985, 292, 105. (b) Grushin, V. V.; Demkina, I. I.;
Tolstaya, T. P. Inorg. Chem. 1991, 30, 4860.
4
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5
ACS Paragon Plus Environment