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Journal of the American Chemical Society
Espino, C. G.; Wehn, P. M.; Chow, J.; Du Bois, J. Synthesis of 1,3–Difunc-
(12) The esp ligand is derived from a,a,a’,a’-tetramethyl-1,3-benzenedi-
1
2
3
4
5
6
7
8
9
tionalized Amine Derivatives through Selective C–H Bond Oxidation. J. Am.
Chem. Soc. 2001, 123, 6935–6936. (c) Espino, C. G.; Fiori, K. W.; Kim, M.;
Du Bois, J. Expanding the Scope of C–H Amination through Catalyst De-
sign. J. Am. Chem. Soc. 2004, 126, 15378–15379. (d) Stokes, B. J.; Dong, H.;
Leslie, B. E.; Pumphrey, A. L.; Driver, T. G. Intramolecular C–H Amination
propionic acid.
(13) (a) Dias, H. V. R.; Polach, S. A.; Goh, S.-K.; Archibong, E. F.; Marynick,
D. S. Copper and silver complexes containing organic azide ligands:ꢀ synthe-
ses, structures, and theoretical investigation of [HB(3,5-
(
CF
(where Pz = Pyrazolyl and 1-Ad = 1-Adamantyl). Inorg. Chem. 2000, 39,
894–3901. (b) Seok, W. K.; Klapötke, T. M. Inorganic and Transition
3
)
2
Pz)
3
]CuNNN(1-Ad) and [HB(3,5-(CF
3
)
2
Pz)
3
]AgN(1-Ad)NN
Reactions: Exploitation of the Rh
acrylates. J. Am. Chem. Soc. 2007, 129, 7500–7501. (e) Nguyen, Q.; Sun, K.;
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2
(II)-Catalyzed Decomposition of Azido-
3
2
Metal Azides. Bull. Korean Chem. Soc. 2010, 31, 781–788.
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Temperature Matrices. Tetrahedron Lett. 1983, 24, 3887–3890.
2
2
Yousufuddin, M.; Devarajan, D.; Ess, D. H.; Kürti, L.; Falck, J.R. Direct and
Stereospecific Synthesis of Unprotected N–H and N–Me Aziridines from
Olefins. Science 2014, 343, 61–65. (g) Paudyal, M. P.; Adebesin, A. M.; Burt,
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arene amination using hydroxylamines. Science 2016, 353, 1144–1147. (h)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(15) Loss of N from 2b to generate 3b could be stimulated both by irradia-
tion with 365 nm light and also by prolonged exposure to synchrotron radi-
ation. In addition to the 50 keV radiation used to acquire the data presented
above, we have examined the structure of 2b as a function of time with both
50 and 37.5 keV radiation without 365 nm irradiation and in both cases ob-
3
Chiappini, N. D.; Mack, J. B. C.; Du Bois, J. Intermolecular C(sp )–H Ami-
nation of Complex Molecules. Angew. Chem. Int. Ed. 2018, 57, 4956–4959.
served N
2
loss to generate 3b·N
2
loss was stimulated. The structure gener-
(
6) Perry, R. H.; Cahill, T. J., III; Roizen, J. L.; Du Bois, J.; Zare, R. N. Cap-
ated by photochemically promoted N loss is identical to that promoted by
X-ray stimulated N
vations made in protein crystallography regarding the cleavage of weak
bonds upon extended irradiation as a mechanism to dissipate incipient X-ray
energy. See, Garman, E. Radiation damage in macromolecular crystallog-
raphy: what is it and why should we care? Acta Cryst. D. 2010, 66, 339–351.
(15) The formation of 3b·N results in the structure evolution from P2 /c to
2
turing fleeting intermediates in a catalytic C–H amination reaction cycle.
Proc. Nat. Acad. Sci. USA 2012, 109, 18295–18299.
2
loss. The X-ray stimulated loss of N is similar to obser-
2
(7) Das, A.; Maher, A. G.; Telser, J.; Powers, D. C. Observation of a Photo-
generated Rh
018, 140, 10412–10415.
8) (a) Harrison, J. G.; Gutierrez, O.; Jana, N.; Driver, T. G.; Tantillo, D. J.
Mechanism of Rh (II,II)-Catalyzed Indole Formation: The Catalyst Does
2
Nitrenoid Intermediate in C–H Amination. J. Am. Chem. Soc.
2
(
2
1
2
P2
0.8913(10), b = 14.274(1), c = 18.732(2), b = 105.847(1), V = 2801.7(4)
to 3b·N : a = 11.030(2) b = 14.251(2), c = 18.763(3), b = 107.025(2), V =
820.2(8)]. This is not a transformation of the monoclinic standard space-
group P2 /c to the nonstandard space group P2 /n [matrix (1 0 1/0 1 0/ -1
0 0), new cell : 18.924, 14.275, 10.891, 107.77].
16) For these calculations, adamantyl groups were truncated as t-butyl
groups. The described computational method has previously been utilized
to evaluate the structures of Rh nitrenoids, see: Valeria-Álvarez, A.; Haines,
/n, with only minor changes in the unit cell parameters [2b: a =
1
Not Control Selectivity. J. Am. Chem. Soc. 2016, 138, 487–490. (b) Varela-
Álvarez, A.; Yang, T.; Jennings, H.; Kornecki, K. P.; Macmillan, S. N.; Lan-
caster, K. M.; Mack, J. B. C.; Du Bois, J.; Berry, J. F.; Musaev, D. G.
1
2
2
Rh (II,III) Catalysts with Chelating Carboxylate and Carboxamidate Sup-
2
1
1
ports: Electronic Structure and Nitrene Transfer Reactivity. J. Am. Chem.
Soc. 2016, 138, 2327–2341. (c) Wang, J.; Zhao, C.; Weng, Y.; Xu, H. Insight
(
II,II
into the mechanism and site-selectivity of Rh
2
(esp) -catalyzed intermo-
2
lecular C–H amination. Catal. Sci. Technol. 2016, 6, 5292–5303.
(9) For examples in the context of reactive metal nitrenoid fragments, see:
2
B. E.; Musaev, D. G. Key mechanistic insights into the intramolecular C–H
bond amination and double bond aziridination in sulfamate esters catalyzed
by dirhodium tetracarboxylate complexes. J. Organomet. Chem. 2018, 867,
(a) Shay, D. T.; Yap, G. P. A.; Zakharov, L. N.; Rheingold, A. L.; Theopold,
K. H. Intramolecular C–H Activation by an Open-Shell Cobalt(III) Imido
Complex. 2005, 44, 1508–1510. (b) Laskowski, C. A.; Miller, A. J. M.; Hill-
house, G. L.; Cundari, T. R. A Two-Coordinate Nickel Imido Complex that
Effects C–H Amination. J. Am. Chem. Soc. 2011, 133, 771–773. (c) Iovan,
D. A.; Betley, T. A. Characterization of Iron-Imido Species Relevant for N-
Group Transfer Chemistry. J. Am. Chem. Soc. 2016, 138, 1983–1993. (d)
Bakhoda, A.; Jiang, Q.; Bertke, J. A.; Cundari, T. R.; Warren, T. H. Elusive
Terminal Copper Arylnitrene Intermediates. Angew. Chem. Int. Ed. 2017, 56,
1
83–192. Computations pursued using the BP86 functional in combination
with the TZVP basis set for Rh and 6-31G** for other atoms (ref. 8b) are
detailed in the Supporting Information.
3
(
[
17) Similarly, [3a] is computed to be 6.9 kcal/mol lower in energy than
3a]. See Supporting Information for details and for discussion of the im-
1
pact of the apical ligand on the structures of Rh
2
nitrenoids.
6
426–6430.
(10) Downs, A. J.; Greene, T. M. Coming to Grips with Reactive Intermedi-
ates. Adv. Inorg. Chem. 1999, 46, 101–171.
(11) Das, A.; Reibenspies, J. H.; Chen, Y.-S.; Powers, D. C. Direct Charac-
terization of a Reactive Lattice-Confined Ru
2
Nitride by Photocrystallog-
raphy. J. Am. Chem. Soc. 2017, 139, 2912–2915.
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