A dianionic, square planar cobalt(II) complex reacts with O_2 in the presence of acetonitrile to give a cyanomethylcobalt(III) complex formed by C-H bond cleavage. Interestingly, PhIO and -tolylazide react similarly to give the same cyanomethylcobalt(III) complex. Competition studies with various hydrocarbon substrates indicate that the rate of C-H bond cleavage greatly depends on the pK_a of the C-H bond, rather than on the C-H bond dissociation energy. Kinetic isotope experiments reveal a moderate KIE value of ca. 3.5 using either O_2 or PhIO. The possible involvement of a cobalt(IV) oxo species in this chemistry is discussed

Hadt, Ryan G.

Nguyen, Andy I.

Solomon, Edward I.

Tilley, T. Don

Caltech Authors - Main

Supporting Information
Efficient C-H Bond Activations via O2 Cleavage by a Dianionic Cobalt(II) Complex
Andy I. Nguyen1, Ryan G. Hadt2, Edward I. Solomon2, T. Don Tilley1*
1Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-
1460.
 2Department of Chemistry, Stanford University, Stanford, California 94305
*Email: tdtilley@berkeley.edu
1.   Experimental Details
General Considerations
All manipulations were carried out using Schlenk techniques[1] under a purified N2 atmosphere 
or in a Vacuum Atmospheres drybox. Solvents (spectroscopic grade) were purchased from 
Aldrich.  Dry THF was prepared by passage through a VAC drying column. Acetonitrile was 
dried with CaH2, and then fractionally distilled from CaH2 under N2. Acetonitrile used for 
crystallization was vacuum transferred from P2O5. n-Butyronitrile (nPrCN) was dried by 
distillation over CaH2. Dry solvents were stored under N2 in Straus flasks. Cobalt(II) chloride, 
potassium hydride, 5-bromo-salicylic acid, ethylenediamine, iodosylbenzene (PhIO), 9,10-
dihydroanthracene, and triphenylphosphine were purchased from Aldrich and used as received. 
NMR spectra were recorded on Bruker AVB-400, AVQ-400 and AV-300 spectrometers at room 
temperature. d3-MeCN and d6-DMSO were purchased from Cambridge Isotopes and dried over 
3Å sieves under N2. 1H NMR spectra were referenced to residual protio solvent peaks (δ 2.94 for 
CD3CN, δ 2.50 for (CD3)2SO). 13C{1H} NMR spectra were referenced to solvent resonances (δ 
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Electronic Supplementary Material (ESI) for Chemical Science.
This journal is © The Royal Society of Chemistry 2014
118.26 for CD3CN, δ 39.51 for (CD3)2SO). Elemental analyses were carried out by the College 
of Chemistry Microanalytical Laboratory at the University of California, Berkeley. Infrared 
spectra were recorded on a Bruker Alpha P attenuated total reflectance instrument. UV-vis 
spectra were obtained on a Varian Cary 300 Bio or Varian Cary 50 BIO UV−visible 
spectrophotometer with a Unisoko cryostat attachment for stirring and temperature control in 1-
cm air-free quartz cells.  X-band electron paramagnetic resonance (EPR) spectra were obtained 
using a Bruker EMX spectrometer. X-band spectra were obtained at 77 K in a liquid nitrogen 
finger dewar using an ER 041 XG microwave bridge and an ER 4102ST cavity (parameters for 
recording the X-band EPR data: 9.63 GHz frequency, 1 mW microwave power, and 10 G 
modulation amplitude). X-band data were simulated using the Easy Spin program. Mass 
spectrometry measurements were performed at the QB3 Mass Spectrometry Facility at UC 
Berkeley using a quadrupole time-of-flight mass spectrometer (Q-TOF Premier, Waters, Milford, 
MA) that was equipped with an electrospray ionization (ESI) source.  ESI source voltages were 
adjusted for optimum desolvation and transmission of ions of interest prior to recording mass 
spectra. Cyclic voltammograms were obtained with a BASi Epsilon potentiostat at room 
temperature using a glassy carbon working electrode (7 mm diameter), a platinum counter 
electrode, and a silver wire floating reference. All potentials were referenced against an 
[Cp2Fe]0/+ internal standard in acetonitrile.
Preparation of (BrHBA-Et)H4, N,N'-(ethane-1,2-diyl)bis(5-bromo-2-hydroxybenzamide).  5-
Bromo-salicylic acid (5.4 g, 25 mmol) was combined with acetic anhydride (5 mL) and sulfuric 
acid (3 drops).  The mixture was heated to 80 °C for 10 min.  Water (100 mL) was added to the 
solid mass and the resulting solid was collected by filtration (5.6 g). The solid was dissolved in 
oxalyl chloride (6 mL) and DMF (2 drops) over 1 h. The volatile materials were removed in 
S2
vacuo and the resulting residue was triturated twice with dichloromethane to give a white solid. 
The solid was dissolved in 100 mL of THF and the resulting solution was cooled to 0 °C.  
Ethylenediamine (0.72 mL, 11 mmol) was added dropwise and the resulting solution was stirred 
for 30 min. Triethylamine (4.5 mL, 32 mmol) in 100 mL of THF was added and the stirring was 
continued for 45 min at room temperature. The solution was filtered and the filtrate was 
evaporated to dryness and then washed with cold ethanol (0°C, 50 mL) to give a white solid. The 
solid from the last filtration was washed with 500 mL of water. The combined solids were 
dissolved in a solvent mixture of 200 mL water / 150 mL ethanol containing 1.5 g (37 mmol) of 
sodium hydroxide.  The solution was refluxed for 30 min and then quenched with 3.5 mL of HCl 
(12.1 M).  The resulting mixture was cooled to 0 °C and then filtered to give the product as a 
white solid (3.12 g, 55%).
1H NMR (400 MHz, d6-DMSO) δ: 3.49 (m, 4H, –CH2CH2–), 6.89 (d, 2H, 3JHH = 8.7, aryl-H), 
7.55 (dd, 2H, 3JHH = 8.7, 4JHH = 2.2, aryl-H), 8.03 (d, 2H, 4JHH = 2.2, aryl-H), 9.01 (t, 2H, 3JHH = 
5.3, N–H), 12.53 (s, 2H, O–H); HRMS (ESI) for C16H13Br2N2O4 [M – H+]– 456.92, found 
456.9214.
Preparation of [nBu4N]2[(BrHBA-Et)Co] ([nBu4N]21).  Potassium hydride (0.102 g, 2.54 
mmol), (BrHBA-Et)H4 (0.292 g, 0.640), and 10 mL of THF were combined in a 20 mL vial, and 
the resulting reaction mixture was stirred for 16 h.  CoCl2 (0.083 g, 0.640 mmol) was then added 
and the dark green solution was stirred for 16 h.  Tetra-n-butylammonium chloride (0.354 g, 1.27 
mmol) was then added and the stirring was continued for 2 h.  The orange precipitate was 
collected by filtration and extracted into 15 mL of acetonitrile.  The extract was evaporated in 
vacuo to give an orange crystalline solid (0.371 g, 58%).  Anal. Calcd for C48H82Br2CoN4O4: C, 
57.77; H, 8.28; N, 5.61. Found: C, 57.17; H, 8.30; N, 5.28. IR (neat) ν/cm–1: 2959, 2931, 2873, 
S3
1577, 1550, 1489, 1460, 1406, 1520, 1326, 1263, 1228, 1143, 1110, 882, 819, 681, 736, 656, 
625, 535, 465, 419. UV-vis (MeCN) λmax/nm (ε/M–1 cm–1): 450 (2200), 320 (17,000), 217 
(62,000). Magnetic Susceptibility (298 K, MeCN) μB: 1.98. 
Preparation of [nMe4N]2[(BrHBA-Et)Co] ([Me4N]21•2CH3CN).  Potassium hydride (0.145 g, 
3.61 mmol), (BrHBA-Et)H4 (0.4127 g, 0.900 mmol), and 10 mL of THF were combined in a 20 
mL vial, and the resulting reaction mixture was stirred for 16 h.  CoCl2 (0.117 g, 0.900 mmol) 
was then added and the resulting green solution was stirred for 3 h.  Tetra-n-methylammonium 
chloride (0.197 g, 1.80 mmol) was then added and stirring was continued for 16 h.  The orange 
precipitate was collected by filtration and extracted into 15 mL of MeCN.  The extract was 
evaporated in vacuo to give an orange crystalline solid (0.293 g, 44%). Anal. Calcd for 
C48H82Br2CoN4O4•2CH3CN: C, 45.24; H, 5.42; N, 11.30. Found: C, 45.0; H, 5.51; N, 11.0.
Preparation of [nBu4N][(BrHBA-Et)Co] ([nBu4N]2).  AgCl (0.0291 g, 0.205 mmol) was added 
to a slurry of [nBu4N]21 (0.205 g, 0.205 mmol) in 10 mL of THF.  The reaction mixture was 
stirred for 45 minutes, and then 3 mL of Et2O was added to precipitate [nBu4N]Cl.  Filtration of 
the reaction mixture through a celite plug and evaporation of the resulting purple solution 
afforded a purple solid (0.155 g, 98%). Figure S1 shows the x-ray crystal structure with selected 
bond lengths.
Anal. Calcd for C32H46Br2CoN3O4: C, 50.87; H, 6.14; N, 5.56. Found: C, 50.0; H, 5.90; N, 5.29. 
1H NMR (400 MHz, CD3CN) δ: -28.05 (s, 2H, aryl-H), 0.72 (t, 12H, 3JHH = 6.5,  
(CH3CH2CH2CH2)4N), 1.05 (sex, 8H, 3JHH = 6.5,  (CH3CH2CH2CH2)4N), 1.28 (br, 8H, 
(CH3CH2CH2CH2)4N), 2.73 (t, 8H, 3JHH = 6.3,  (CH3CH2CH2CH2)4N), 19.00 (s, 2H, aryl-H), 
29.93 (s, 2H, aryl-H), 318.04 (s, 2H, –CH2CH2–). IR (neat) ν/cm–1: 2956, 2931, 2868, 1580, 
1552, 1520, 1456, 1409, 1298, 1145, 1093, 882, 821, 740, 685, 630, 583, 538, 487, 464, 424. 
S4
UV-vis (MeCN) λmax/nm (ε/M–1 cm–1): 560 (6800), 378 (3000), 303 (10,000), 250 (15,000), 214 
(38,000). Magnetic Susceptibility (298 K, MeCN) μB: 2.88.
Figure S1. ORTEP diagram of [nBu4N]22. Thermal ellipsoids are drawn at 50%, hydrogen atoms 
and nBu4N+ cations are omitted for clarity.  Selected bond distances (Å) and angles (deg) for [1]: 
N(1)–Co(1) 1.834(2), N(2)–Co(1) 1.836(2), O(1)–Co(1) 1.831(2), O(2)–Co(1) 1.830(2); O(2)–
Co(1)–N(2) 94.90(9), N(2)–Co(1)–N(1) 86.41(10), N(1)–Co(1)–O(1) 95.22(9), O(2)–Co(1)–
O(1) 83.98(8).
Preparation of [nBu4N]2[(BrHBA-Et)Co(CH2CN)] ([nBu4N]23).  A MeCN solution (5 mL) of 
[nBu4N]21 (0.107 g, 0.107 mmol) in a Schlenk tube was degassed with one freeze-pump-thaw 
cycle, and this solution was exposed to 1 atm of dry O2 at room temperature.  The reaction 
mixture was stirred for 2 h at room temperature to produce a dark brown solution. The volatile 
materials were removed in vacuo to afford a brown residue.  The residue was dissolved in 3 mL 
of THF, and 3 mL of Et2O was added to yield a green oily residue and a purple solution.  The 
purple solution was decanted away from the oil, and evaporated in vacuo to give [nBu4N][2] 
(0.010 g, 12% based on [nBu4N]21), identified by 1H NMR spectroscopy. The green oil was 
stirred vigorously in 10 mL of Et2O to give [nBu4N]23 as a green solid, which was collected by 
filtration (0.056 g, 50% based on [nBu4N]21).  Single crystals suitable for X-ray diffraction were 
obtained by vapor diffusion of Et2O into a saturated solution of [nBu4N]23 in THF. 
S5
Anal. Calcd for C50H84Br2CoN5O4: C, 57.86; H, 8.16; N, 6.75. Found: C, 57.58; H, 8.05; N, 7.07. 
1H NMR (400 MHz, CD3CN) δ: 0.93 (t, 24H, 3JHH = 6.8, (CH3CH2CH2CH2)4N), 1.31 (sex, 16H, 
3JHH = 6.8, (CH3CH2CH2CH2)4N), 1.53 (br, 16H, (CH3CH2CH2CH2)4N), 1.54 (s, 2H, CH2CN) 
3.04 (br, 16H, (CH3CH2CH2CH2)4N), 3.50 (m, 4H, –CH2CH2–), 6.93 (d, 2H, 3JHH = 8.4, aryl-H), 
6.98 (dd, 2H, 3JHH = 8.4, 4JHH = 2, aryl-H), 8.01 (d, 2H, 4JHH = 2, aryl-H). 13C{1H} NMR (100.62 
MHz, CD3CN) δ: 13.72 ((CH3CH2CH2CH2)4N), 20.30 ((CH3CH2CH2CH2)4N), 24.20 
((CH3CH2CH2CH2)4N), 50.34 (–CH2CH2–), 59.15 ((CH3CH2CH2CH2)4N), 104.15 (aryl-C), 
126.33 (aryl-C), 131.89 (aryl-C), 133.26 (aryl-C), 169.59 (aryl-C), 170.96 (C=O). IR (neat) 
ν/cm–1: 2961, 2931, 2873, 2203 (C≡N), 1580, 1552, 1520, 1452, 1409, 1309, 1261, 1228, 1145, 
1108, 1093, 1025, 882, 819, 739, 680, 648, 628, 535, 465, 440, 423. UV-vis (MeCN) λmax/nm 
(ε/M–1 cm–1): 800 (1300), 217 (68,000).
Generation of [nBu4N]2[(BrHBA-Et)Co(CH2CN)] ([nBu4N]23) by stoichiometric O2.  In a J. 
Young tube, [nBu4N]21 (0.031 g, 0.031 mmol) was dissolved in 0.6 mL of CD3CN.  The solution 
was degassed by a freeze-pump-thaw cycle. A rubber septum with a needle was fitted on the J. 
Young tube and the headspace was degassed by pulling vacuum. A syringe containing 0.2 mL 
dry O2 (0.0078 mmol) was inserted into the septum, and the J. Young seal was opened to allow 
the O2 to diffuse into the tube. The reaction was complete after 16 h, and [nBu4N]23 was formed 
along 88% yield by 1H NMR spectroscopy (with respect to [nBu4N]21), using 1,4-
dimethoxybenzene or [nBu4N]+ as an internal standard.  
Generation of [nBu4N]2[(BrHBA-Et)Co(CH2CN)] ([nBu4N]23) by PhIO.  In a J. Young tube, 
[nBu4N]21 (0.037 g, 0.037 mmol) and PhIO (0.0041 g, 0.018 mmol) were dissolved in 0.6 mL of 
CD3CN.  The reaction was complete after 16 h, and [nBu4N]23 was formed along with 
S6
iodobenzene in quantitative yield by 1H NMR spectroscopy (with respect to both iodosylbenzene 
and [nBu4N]21), using 1,4-dimethoxybenzene or [nBu4N]+ as an internal standard.  
Generation of [nBu4N]2[(BrHBA-Et)Co(CH2CN)] ([nBu4N]23) by [nBu4N]IO4.  In a J. Young 
tube, [nBu4N]21 (0.050 g, 0.050 mmol) was dissolved in ~1 mL of CD3CN, and [nBu4N]IO4 
(0.010 g, 0.025 mmol) was added slowly in small batches with stirring.  The reaction was 
complete after 0.5 h, and [nBu4N]23 was formed in near quantitative yield (96% with respect to 
[nBu4N]21) by 1H NMR spectroscopy, using either 1,4-dimethoxybenzene (0.0055g) or [nBu4N]+ 
as an internal standard.  A spectrum of this reaction is shown below as a representative of all 1H 
NMR spectroscopy reactions in this paper:
Preparation of [nBu4N]2[(BrHBA-Et)Co(CCPh)] ([nBu4N]24).  To a MeCN solution (5 mL) of 
[nBu4N]21 (0.100 g, 0.107 mmol) was added phenylacetylene (0.102 g, 1.10 mmol).  
Iodosylbenzene (0.011 g, 0.050 mmol) was added, and the resulting reaction mixture was stirred 
S7
for 3 h.  Diethyl ether (15 mL) was added to the solution and a green crystalline solid formed 
overnight.  The mother liquor was decanted and the solid was dried in vacuo to yield 0.084 g 
(76%) of the product.
1H NMR (400 MHz, CD3CN) δ: 0.92 (br, 24H, (CH3CH2CH2CH2)4N), 1.29 (br, 16H, 
(CH3CH2CH2CH2)4N), 1.52 (br, 16H, (CH3CH2CH2CH2)4N), 3.03 (br, 16H, 
(CH3CH2CH2CH2)4N), 3.45 (m, 2H, –CH2CH2–), 3.67 (m, 2H, –CH2CH2–), 6.84–7.00 (m, 9H, 
aryl-H), 8.04 (br, 2H, aryl-H). 13C{1H} NMR (100.62 MHz, CD3CN) δ: 13.85 
((CH3CH2CH2CH2)4N), 20.29 ((CH3CH2CH2CH2)4N), 24.29 ((CH3CH2CH2CH2)4N), 51.15 (–
CH2CH2–), 59.14 ((CH3CH2CH2CH2)4N), 105.28 (aryl-C), 114.93 (PhC≡C–), 125.51 (aryl-C), 
125.83 (aryl-C), 127.26 (aryl-C), 128.83 (aryl-C), 132.24 (aryl-C), 132.93 (aryl-C), 133.04 (aryl-
C), 168.94 (aryl-C), 171.41 (C=O). IR (neat) ν/cm–1: 2958, 2934, 2870, 2106 (C≡C), 1576, 1555, 
1519, 1458, 1440, 1410, 1317, 1265, 1229, 878, 814; HRMS (ESI) for C24H15Br2CoN2O4 [M]2– 
m/z = 306.94, found 306.94.
Generation of [nBu4N]2[(BrHBA-Et)Co(CCPh)] ([nBu4N]24) by O2. A J. Young tube 
containing [nBu4N]21 (0.025 g, 0.025 mmol) and phenylacetylene (0.026 g, 0.25 mmol) was 
degassed by one freeze-pump-thaw cycle.  Excess dry O2 (1 atm) was added to the reaction 
mixture. After 1 h, a green solution was obtained.  1H NMR spectroscopy showed quantitative 
formation of [nBu4N]24 by integration against 1,4-dimethoxybenzene internal standard (0.003 g, 
0.022 mmol).
Reaction of [nBu4N]21, KIO3, and 18-crown-6 in MeCN. Potassium iodate (0.005 g, 0.025 
mmol) was added to a MeCN solution (0.6 mL) containing [nBu4N]21 (0.050 g, 0.050 mmol) and 
18-crown-6 (0.006 g, 0.025 mmol).  The reaction was allowed to react for 16 h.  No color change 
was observed indicating no generation of [nBu4N]23.
S8
Reaction of [nBu4N]21, PhIO, and cyclohexene. PhIO (0.011 g, 0.050 mmol) was added to a d3-
MeCN solution (0.6 mL) containing [nBu4N]21 (0.050 g, 0.050 mmol) and excess cyclohexene 
(0.042 g, 0.50 mmol).  The reaction was allowed to react for 16 h, and analyzed by 1H NMR 
spectroscopy which showed a 46% yield of [nBu4N]23, and no change in cyclohexene integration 
(no new shifts corresponding to any new organic products were observed either) using [nBu4N]+ 
as an internal standard.  Gas-chromatography mass spectrometry only showed peaks for 
cyclohexene, 1,4-dimethoxybenzene, and iodobenzene.
Reaction of [nBu4N]21, O2, and 9,10-dihydroanthracene. Excess O2 was added to a d3-MeCN 
slurry (0.6 mL) containing [nBu4N]21 (0.0403 g, 0.0404 mmol) and 9,10-dihydroanthracene 
(0.072 g, 0.404 mmol).  The reaction mixture was analyzed by 1H NMR spectroscopy after 24 h, 
which showed a 12% yield of anthraquinone using [nBu4N]+ as an internal standard.
Reaction of [nBu4N]21, PhIO, and 9,10-dihydroanthracene. PhIO (0.004 g, 0.020 mmol) was 
added to a d3-MeCN slurry (0.6 mL) containing [nBu4N]21 (0.020 g, 0.020 mmol) and 9,10-
dihydroanthracene (0.036 g, 0.20 mmol).  The reaction mixture was analyzed by 1H NMR 
spectroscopy after 45 minutes, which showed a 13% yield of anthracene using [nBu4N]+ as an 
internal standard.
UV-vis measurement of [nBu4N]21 + O2. Dry O2 (1 atm) was added to a Teflon sealed, air-tight 
quartz cuvette containing a solution of [nBu4N]21 in 1:1 MeCN/THF (3.0 mL, 8.5 x 10–5 M) at –
63°C.  A measurement was taken every minute for 60 minutes from the point of O2 addition.  To 
record the spectrum of the completed reaction, the cuvette was then allowed to warm up to room 
temperature for 10 minutes, and then cooled back down to –63°C before the spectrum was 
recorded.
S9
Preparation of [6]2– ESI-MS sample. Dry O2 was added via a blunt syringe to a vial capped 
with a rubber septum containing a solution of [Me4N]21 in MeCN (1 mM).  At room 
temperature, an aliquot from the reaction mixture was analyzed after approximately 30 s. Figure 
S2 shows the full spectrum and inset shows the zoomed up region for [6]2–.
Figure S2. Negative-ion ESI-MS (full and close up of region-of-interest). Other ions identified 
are: (a) 227.96, [LH2]2-, (b) 378.86, [LH4(-Br)]-, (c) various monobrominated complexes, 
indicated by a doublet pattern (debromination in ESI), (d) 485.39, [(LH2)2CoII]2-, (e) [2]-, (f) 
528.83, [LCoO]-, (g) 580.93, [(LCoII)(Me4N)]-, (h) 632.93, [(LH)CoII(formate)(Me4N)]-, (i) 
678.94, [(LH2)CoII(formate)2(Me4N)]-, (j) 696.04, [(LCoII)(H2O)(OH)(Me4N)2]-. No peaks could 
be assigned to the species [LCoIIIOH]2-, [(LCoIII)2O]4-, [LCoIIIO2]-, ([LCoIII)2O2]4-, or their 
adducts with either Na+ or Me4N+.  (L= [BrHBA-Et]4-)
*Note: Relative abundance is not representative of relative concentrations in solution.
S10
Preparation of [nBu4N]21 EPR sample. A solution of [nBu4N]21 in nPrCN (5 mM) in a quartz 
EPR tube was prepared.  The solution was cooled to 77 K.  Figure S3 shows the simulated and 
experimental EPR spectrum.
Figure S3.  Simulated and experimental spectrum for [1]2–.
Observation of [5]2– generated from O2, by EPR. Dry O2 was added to a quartz EPR tube 
capped with a rubber septum containing a solution of [nBu4N]21 in nPrCN (5 mM).  The reaction 
mixture was maintained at room temperature for approximately 30 s and then was immediately 
cooled to 77 K. Figure S4 shows the simulated and experimental EPR spectrum.
S11
Figure S4. Simulated and experimental spectrum for [5]2–.
Reversible formation of [5]2– observed by EPR.  An EPR spectrum was acquired of a Teflon 
sealed J. Young tube containing a solution of [nBu4N]21 in MeCN (5 mM).  The solution was 
degassed by one freeze-pump-thaw cycle and dry O2 was added to the vessel and the reaction 
mixture was maintained at room temperature for approximately 60 s, and then it was rapidly 
cooled to 77 K and an EPR spectrum was acquired. The solution was then degassed by one 
freeze-pump-thaw cycle, cooled to 77 K, and an EPR spectrum was acquired.  Figure S5 shows 
the overlay of the two spectra.
S12
Figure S5. EPR spectra of the reaction mixture before O2 addition, after O2 addition, and after 
degassing.
Analysis of complete reaction mixture ([nBu4N]21 + O2) by EPR. Dry O2 was added to a 
quartz EPR tube capped with a rubber septum containing a solution of [nBu4N]21 in nPrCN (5 
mM).  The reaction was allowed to occur at room temperature for approximately 10 min, and the 
reaction mixture was then rapidly cooled to 77 K.
S13
Preparation of [nBu4N]21 sample for cyclic voltammetry.  A solution of [1]2– (1.04 x 10-3 M, 
10 mL) in 0.10 M tetra-n-butylammonium hexafluorophosphate acetonitrile solution was 
prepared in a N2 filled glovebox at room temperature. Potentials were then referenced to 
ferrocene internal standard.
Figure S6.  Cyclic voltammagram of [nBu4N]21 at 100 mv/s (without ferrocene).
3.   X-ray Crystallography Details
X-ray diffraction data were collected using Bruker AXS three-circle diffractometers coupled to a 
CCD detector with either QUAZAR multilayer mirror- or graphite-monochromated Mo Kα 
radiation (λ = 0.71073 Å). The structures were solved by direct methods using SHELXS and 
refined against F2 on all data by full-matrix least squares with SHELXL-97. All non-hydrogen 
atoms were refined anisotropically; hydrogen atoms were included into the model at their 
geometrically calculated positions and refined using a riding model.
S14


Efficient C-H Bond Activations  O_2 Cleavage by a Dianionic Cobalt(II) Complex

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Efficient C-H Bond Activations O_2 Cleavage by a Dianionic Cobalt(II) Complex

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