Journal of the American Chemical Society
Article
(
6) For isolated examples of bis-perfluoroalkyl NiIII that are not
(20) Zhang, C. P.; Wang, H.; Klein, A.; Biewer, C.; Stimat, K.;
Yamaguchi, Y.; Xu, L.; Gomez-Benitez, V.; Vicic, D. A. J. Am. Chem.
Soc. 2013, 135, 8141.
(21) Xu, H.; Diccianni, J. B.; Katigbak, J.; Hu, C.; Zhang, Y.; Diao, T.
J. Am. Chem. Soc. 2016, 138, 4779.
reported to undergo C−C coupling, see: (a) Tang, F.; Rath, N. P.;
Mirica, L. M. Chem. Commun. 2015, 51, 3113. (b) Yu, S.; Dudkina, Y.;
Wang, H.; Kholin, K. V.; Budnikova, V.; Kadirov, M. K.; Vicic, D. A.
Dalton Trans. 2015, 44, 19443.
(
IV
7) For a related mono-aryl Ni complex, see: Espinosa-Martinez,
(22) For the formation of tetraphenylene from metallacyclofluorenes,
see: (a) Schwager, H.; Spyroudis, S.; Vollhardt, K. P. C. J. Organomet.
Chem. 1990, 382, 191. (b) Edelbach, B. L.; Lachicotte, R. J.; Jones, W.
D. J. Am. Chem. Soc. 1998, 120, 2843. (c) Simhai, N.; Iverson, C. N.;
Edelbach, B. L.; Jones, W. D. Organometallics 2001, 20, 2759.
(d) Beck, R.; Johnson, S. A. Chem. Commun. 2011, 47, 9233.
(23) The other identifiable organic product of this reaction is
biphenyl, which is formed in ≤4% yield, depending on the reaction
conditions.
G.; Ocampo, C.; Park, Y. J.; Fout, A. R. J. Am. Chem. Soc. 2016, 138,
290.
8) (a) Grove, D. M.; van Koten, G.; Zoet, R.; Murrall, N. W.; Welch,
4
(
A. J. J. Am. Chem. Soc. 1983, 105, 1379. (b) Grove, D. M.; van Koten,
G.; Mul, W. P.; van der Zeijden, A. A. H.; Terheijden, J.; et al.
Organometallics 1986, 5, 322. (c) Grove, D. M.; van Koten, G.; Mul,
P.; Zoet, R.; van der Linden, J. G. M.; Legters, J.; Schmitz, J. E. J.;
Murral, N. W.; Welch, A. J. Inorg. Chem. 1988, 27, 2466. (d) van de
Kuil, V. A.; Veldhuizen, Y. S. J.; Grove, D. M.; Zwikker, J. L.;
Jenneskens, L. W.; Drenth, W.; Smeets, W. J. J.; Spek, A. L.; van
Koten, G. J. Organomet. Chem. 1995, 488, 191. (e) Higgs, A. T.; Zinn,
P. J.; Simmons, S. J.; Sanford, M. S. Organometallics 2009, 28, 6142.
0
(24) Gray and black precipitates consistent with Ni were observed in
these reactions.
(
(
25) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1997, 119, 8135.
26) Alternatively, a CF ligand could be transferred directly from 1
3
equiv of 2e to a second equiv of 2e to form 4, without the
(
9) (a) Pandarus, V.; Zargarian, D. Organometallics 2007, 26, 4321.
b) Castonguay, A.; Beauchamp, A.; Zargarian, D. Organometallics
008, 27, 5723. (c) Spasyuk, D. M.; Zargarian, D.; van der Est, A.
intermediacy of F C•.
(
3
(
27) Shi, G.; Shao, C.; Pan, S.; Yu, J.; Zhang, Y. Org. Lett. 2015, 17,
8.
28) The wide peak-to-peak separation of 856 mV is likely due to an
2
3
Organometallics 2009, 28, 6531. (d) Spasyuk, D. M.; Gorelsky, S. I.;
van der Est, A.; Zargarian, D. Inorg. Chem. 2011, 50, 2661.
e) Mougang-Soume,
metallics 2014, 33, 5990.
(
(
electron-transfer chemical (EC) reaction mechanism, wherein
(
́ ́
B.; Belanger-Gariepy, F.; Zargarian, D. Organo-
IV
oxidation to Ni triggers the association of a solvent molecule to
form a more stable octahedral product.
10) Tsou, T. T.; Kochi, J. K. J. Am. Chem. Soc. 1978, 100, 1634.
11) (a) Camasso, N. M.; Sanford, M. S. Science 2015, 347, 1218.
(
29) Notably, NOBF4 was very recently used by Mirica for
(
III
IV
converting organometallic Ni complexes to their Ni analogues
ref 4).
30) The addition of acetylferrocenium tetrafluoroborate (∼0.3 V vs
(
b) Bour, J. R.; Camasso, N. M.; Sanford, M. S. J. Am. Chem. Soc. 2015,
37, 8034.
12) (a) Eisch, J. J.; Piotrowski, A. M.; Han, K. I.; Kru
H. Organometallics 1985, 4, 224. (b) Carmona, E.; Gutier
(
1
(
(
̈
ger, C.; Tsay, Y.
rez-Puebla,
+
Fc/Fc ) also induced Ph−CF coupling from 2e at room temperature
́
3
(
in 98% yield). However, oxidation with this oxidant was slow and no
E.; Marín, J. M.; Monge, A.; Paneque, M.; Poveda, M. L.; Ruíz, C. J.
Am. Chem. Soc. 1989, 111, 2883. (c) Dubinina, G. G.; Brennessel, W.
W.; Miller, J. L.; Vicic, D. A. Organometallics 2008, 27, 3933. (d) Jover,
J.; Miloserdov, F. M.; Benet-Buchholz, J.; Grushin, V. V.; Maseras, F.
Organometallics 2014, 33, 6531. (e) Yamamoto, T.; Abla, M.;
Murakami, Y. Bull. Chem. Soc. Jpn. 2002, 75, 1997.
IV
19
Ni intermediates were detected by F NMR spectroscopy.
31) The initial rates studies were conducted in benzene rather than
(
MeCN because the reaction affords comparable yield (54%) in
benzene but is cleaner (i.e., affords fewer minor side products). The
addition of 15 equiv of MeCN to the reaction of 2e in benzene had
−
7
minimal impact on the initial rate of this reaction (rate = 2.66 × 10
(
13) The CV scan rate had minimal impact on peak-to-peak
−7
mM/h without MeCN and 2.42 × 10 mM/h with MeCN at 0.02 M
concentration of 2e).
separation or peak height ratio in these systems. See Supporting
Information for complete CV data.
(
(
(
(32) We are unable to rule out a mechanism wherein a rate-
14) Geiger, W. E. Organometallics 2007, 26, 5738.
determining ligand dissociation precedes disproportionation. However,
the >50% yield observed at high temperature and the absence of 1e in
the reaction mixture are inconsistent with this pathway.
15) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877.
I
II
16) Ag salts also have been used previously to oxidize Ni
III
complexes to Ni . See refs 6a and 6b.
(
(
33) An order of 0.8 is also obtained when these data are processed
as a log−log plot. See Figure S21b.
34) (a) Mann, G.; Shelby, Q.; Roy, A. H.; Hartwig, J. F.
17) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.;
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09,
revision A.02; Gaussian, Inc.: Wallingford, CT, 2009.
(
Organometallics 2003, 22, 2775. (b) Mann, G.; Baranano, D.;
Hartwig, J. F.; Rheingold, A. L.; Guzei, I. A. J. Am. Chem. Soc. 1998,
1
́
20, 9205. (c) Perez-Temprano, M. H.; Racowski, J. M.; Kampf, J. W.;
Sanford, M. S. J. Am. Chem. Soc. 2014, 136, 4097. (d) Racowski, J. M.;
Dick, A. R.; Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 10974.
(
35) The addition of 3 equiv of pyridine, PPh , and PMe to the
3 3
thermolysis of 2e led to 33%, 40%, and 1% of Ph−CF , respectively.
3
(
36) The recrystallization of 2e in the presence of PMe yielded the
3
corresponding octahedral PMe -ligated 2e, as determined by X-ray
3
crystallography (see Supporting Information).
(37) For example, during the revision of this manuscript, Mirica
reported that C−C reductive elimination from the octahedral complex
4
III
(
N )Ni (CH CMe -o-C H ) is very low yielding (∼10% yield of 3,3-
2
2
6
4
dimethylbenzocylobutane; ref 4). When compared to the reactivity of
a, this suggests that the reactivity of octahedral Ni complexes may
(
18) Computation employed the ucam-B3LYP functional for
geometry optimization utilizing the SDD basis set on Ni and the 6-
1G(d) basis set for other atoms. Spin densities > 0.02 are noted at Ni
III
2
be different from their five-coordinate analogues.
3
(
1.00 to 1.18), Naxial (0.07 to 0.09), NMeCN (−0.05), C bonded to Ni
(−0.05 to −0.18). See Supporting Information for full details.
(
19) TEMPO−CF was found to decompose under these conditions.
3
As such, the observed yield of TEMPO−CF at the end of the reaction
3
(
4%) is likely not representative of the total amount of TEMPO−CF
3
formed throughout the reaction.
G
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX