A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex

Article abstract of DOI:10.1021/jacs.6b05942

Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru - Ru=O intermediate. The most promising candidate, Ru₂(chp)₄ONO

Full text of DOI:10.1021/jacs.6b05942

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Article
A Synthetic Oxygen Atom Transfer Photocycle
from a Diruthenium Oxyanion Complex
Amanda R. Corcos, József S. Pap, Tzuhsiung Yang, and John F. Berry
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b05942 • Publication Date (Web): 13 Jul 2016
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A Synthetic Oxygen Atom Transfer Photocycle
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from a Diruthenium Oxyanion Complex
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Amanda R. Corcos,† József S. Pap,†,‡ Tzuhsiung Yang,† and John F. Berry*,†
† Department of Chemistry, University of Wisconsin – Madison, 1101 University Ave., Madison,
Wisconsin, 53706, USA
ABSTRACT.
Three new diruthenium oxyanion complexes have been prepared, crystallographically
characterized, and screened for their potential to photochemically unmask a reactive Ru–Ru=O
intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-
hydroxypyridinate), displays a set of signals centered around m/z = 733 amu in its MALDI-TOF
mass spectrum, consistent with the formation of the [Ru2(chp)4O]+ ([6]+) ion. These signals shift
18
to 735 amu in 4*, which contains O-labeled nitrate. EPR spectroscopy and headspace GC-MS

analysis indicate that NO2 is released upon photolysis of 4, also consistent with the formation of
an Ru2(chp)4O species. Photolysis of 4 in CH2Cl2 at room temperature in the presence of excess

PPh3 yields OPPh3 in 173% yield; control experiments implicate Ru2(chp)4O (6), NO2 , and free
–
NO3 as the active oxidants. Notably, Ru2(chp)4Cl (3) is recovered after photolysis. Since 3 is the
direct precursor to 4, the results described herein constitute the first example of a synthetic cycle
for oxygen atom transfer that makes use of light to generate a putative metal oxo intermediate.
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INTRODUCTION.
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The use of light in chemical synthesis is a topic of significant current interest.1 We2 and
others3 have recently used light to access putative, highly reactive transition metal-containing
intermediates. The most well-known examples are metal nitride compounds (I), which can be
photochemically accessed from metal azide precursors (Scheme 1).4 Metal terminal oxo species
(II) are related reactive intermediates that are of great importance for biological and synthetic
oxidation reactions.5 Typically, chemical or electrochemical redox reactions5a,6 are used to access
II, but here we probe the possibility of photochemically unmasking a highly reactive species II,
as in the bottom of Scheme 1.
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Scheme 1. Formation of mononuclear metal nitride and oxo species after exposure of metal
azides and oxyanions to light, respectively.
Important precedents for this work include the elimination of nitrite ion from an O=Ru–
ONO2 complex to produce a dioxo Ru species7 and disproportionation of nitrite to form both
Ru=O and Ru–NO complexes.8 Furthermore, Suslick9 and Vogler10 have reported formation and
reactivity of metal oxo species by photolytic cleavage of complexes with O-coordinated
oxyanions, while Newcomb11 and Bakac12 have used flash photolysis to observe similar, highly
reactive species. A major difficulty hindering the synthetic utility of this approach is the question
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of how to regenerate the M–OEOx precursor (Scheme 2). This transformation, shown with a
question mark in Scheme 2, is problematic because substrate (S) oxidation yields a
coordinatively unsaturated metal complex that is reduced by one-electron from the original M–
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–
OEOx species. Installation of OEOx with concomitant one-electron oxidation is problematic
–
because the OEOx ions themselves can act as two-electron oxidants. We report here a solution to
this problem that makes use of the properties of metal-metal bonded compounds.
Scheme 2. Possible stoichiometric cycle illustrating the synthetic limitations of current oxyanion
systems.
We recently described the first examples of M–M=O species (in which M = Mo or W)
and we found them to display unusual reactivity.13 Related Ru–Ru=O intermediates have
recently been proposed to be important in sulfide oxygenation14 and water oxidation15 catalysis;
furthermore, Ru2(II/II) complexes have been shown to reversibly bind O2.16 Putative Ru–Ru=O
species are highly reactive and have not been observed or isolated. Due to their important
catalytic applications and our previous expertise in the chemistry of Ru–RuN intermediates, we
sought to use the photochemical methods outlined above to access Ru–Ru=O species in order to
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explore their fundamental reactivity. We also find the Ru–Ru=O species to be unstable, but it can
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nonetheless be utilized in a synthetic photocycle for oxygen atom transfer.
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RESULTS AND DISCUSSION.
To date, only two discrete (non-polymeric) Ru2 compounds bearing axial oxyanionic
ligands are known: Ru2(DMBA)4(ONO2)2 (DMBA = N,N’-dimethylbenzamidinate),17 which
contains two η1-coordinated nitrate ligands, and Ru2(OAc)4(ONO2)(H2O),18 which forms
polymeric chains upon loss of the aquo ligand. We are instead keen to explore whether a
discrete, anhydrous mono-oxyanion complex with an Ru–Ru–O–EOx structure could be
prepared. As such we turned to the DPhF (DPhF = N,N’-diphenylformamidinate) and chp (chp =
6-chloro-2-hydroxypyridinate) ligands, for their steric bulk near the axial coordination site
should eliminate the possibility of forming polymeric chains and only one oxyanionic ligand
should bind to the Ru2 core based on charge balance. The compounds discussed herein are given
in Chart 1.
Chart 1. Compounds discussed herein.
Entry
Complex
Ligands
Ru2(DPhF)4Cl
1
[Ru2(DPhF)4][NO3]
Ru2(chp)4Cl
2
3
4
5
Ru2(chp)4ONO2
Ru2(chp)4OClO3
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Synthesis and IR Spectroscopic Characterization. Compounds 2, 4, and 5 were prepared
from the chloride precursors 1 and 3 by metathesis with the appropriate Ag+ salts (AgNO3 for 2
and 4; AgClO4 for 5) as seen in Scheme 3. The IR spectrum for 2 displays a signal at 1773 cm-1,
which is well within the characteristic range of 1700-1800 cm-1 for free nitrate anions.19
Furthermore, the MALDI-TOF mass spectrum of 2 shows an isotopic envelope indicative of the
free [Ru2(DPhF)4]+ core (Figure S1), and the crystal structure of 2 consists of well-separated
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–
[Ru2(DPhF)4]+ cations and NO3 anions.20 The steric bulk of the DPhF phenyl rings therefore
–
prevents NO3 coordination. In contrast, the IR spectra of 4 and 5 display signals consistent with
O-coordinated nitrate19b and perchlorate ligands19b,21 (1278 cm-1 [νasym (ONO)] for 4; ν4 = 1154,
1134, 1025 cm-1, and ν2 = 894 cm-1 for 5).
Scheme 3. Formation of nitrate complex 2 from chloride precursor 1 and oxyanion complexes 4
and 5 from chloride precursor 3.
Crystallography. Compounds 4 and 5 have been characterized by X-ray crystallography
(Figures 1, 2 and Table S1). As with the chloride precursor 322 and azide analog Ru2(chp)4N3,2d
the equatorial chp ligands in 4 and 5 are bound in a (4,0) orientation, which allows for the
oxyanionic ligand to bind only to the exposed Ru axial site.
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Figure 1. Thermal ellipsoid plot of 42CH2Cl2 with ellipsoids drawn at the 50% probability
level. Hydrogen atoms and molecules of solvation are omitted for clarity.
Figure 2. Thermal ellipsoid plot of 52CH2Cl2 with ellipsoids drawn at the 50% probability
level. Hydrogen atoms and molecules of solvation are omitted for clarity.
The Ru–Ru distances in 4 and 5 (2.2633(3) Å and 2.2540(7) Å,23 respectively, listed in
5+
Table 1) are in accord with all other previously characterized Ru2 oxypyridinate complexes.24
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The Ru(2)–Ru(1)–O(5) bond angle in 4 deviates from linearity to 170.07(7)° and that in 5
deviates to 170.9(2)°, likely due to crystal packing effects. At 1.221(3) Å and 1.236(3) Å, the
nitrate N–O distances (N(5)–O(6) and N(5)–O(7), respectively) in 4 are slightly shorter than, but
in line with, those of an unbound nitrate anion (1.241(2) Å).25 At 1.306(3) Å, the O(5)–N(5)
distance is significantly longer, causing the nitrate anion to lose 3-fold symmetry due to the
Ru(1)–O(5) interaction. The O(6)–N(5)–O(7) angle is 122.1(3)° and, when combined with the
other O–N–O angles (118.4(3)° and 119.4(2)°), sum to 359.9°, indicating a planar nitrate group,
which is oriented parallel to the Ru–Ru bond. The perchlorate anion in 5 exhibits O–Cl–O angles
that range from 107.0(3)° – 112.8(4)°, which are close to the idealized geometry of 109.5° for a
tetrahedral anion. The O(5)–Cl(5) distance is slightly elongated at 1.464(4) Å compared to the
other O–Cl bond distances of 1.370(5) Å, 1.392(5) Å, and 1.445(6) Å.
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Table 1. Selected crystallographic bond lengths and angles for 4 and 5. E = N for 4, Cl for 5.
Compound
Ru(1)–Ru(2) Å
Ru(1)–O(5) Å
O(5)–E(5) Å
4
5
2.2633(3)
2.200(2)
1.306(3)
1.221(3)
1.236(3)
–
2.2540(7)
2.249(4)
1.464(4)
1.445(6)
1.370(5)
1.392(5)
170.9(2)
E(5)–O(6) Å
E(5)–O(7) Å
E(5)–O(8) Å
Ru(2)–Ru(1)–O(5) (°)
170.07(6)
UV/Vis Spectroscopy. The most intense absorption feature for compounds 3-5 in CH2Cl2
shifts from 529 to 532 to 542 nm and increases in intensity as the coordinating strength of the
anion increases (5 < 4 < 3) (Figure 3). Though this electronic transition has not been definitively
assigned, the variation in energy and intensity observed here suggests that it has significant
LMCT character involving the axial ligand. The secondary feature in the spectrum also shifts
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from 666 to 678 to 689 nm in the same manner (5 < 4 < 3), but the intensity of this feature
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remains relatively consistent throughout the series.
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Figure 3. UV/Vis for compounds 3-5 in CH2Cl2. The spectrum for 3 was previously reported22
but is included here for direct comparison.
Cyclic Voltammetry. Cyclic voltammograms of 4 and 5 were recorded under two distinct
sets of conditions. Solutions of 3-5 in CH2Cl2 with 0.1 M NBu4PF6 electrolyte were examined, as
well as solutions of 4 in 0.1 M NBu4NO3 and 5 in 0.1 M NBu4ClO4. These varying conditions
–
–
give insight into the binding of NO3 and ClO4 anions to the [Ru2(chp)4]+ core in solution. In
–
–
analyzing these data, we can consider two limiting cases. If, first, the NO3 and ClO4 anions
dissociate completely from 4 and 5 in CH2Cl2, then we would expect both compounds to have
–
–
identical CV traces in 0.1 M NBu4PF6. If, on the other hand, we assume that NO3 and ClO4 do
not dissociate at all from 4 or 5 in solution, then we would expect the CV traces of 4 with
NBu4PF6 and NBu4NO3 electrolytes to be identical, and the CV traces of 5 with NBu4PF6 and
NBu4ClO4 to be identical as well. The data shown in Figure 4 (see also Table 2) show clearly
that neither of these limiting cases reflects reality. The fact that the CVs of 4 and 5 in NBu4PF6
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appear distinct indicates that these solutions do not simply contain free [Ru2(chp)4]+ cations.
However, the fact that the redox potentials change when the electrolyte is changed to NBu4NO3
or NBu4ClO4 indicates that both 4 and 5 undergo the following equilibrium in solution:
3
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. Other diruthenium compounds show similar behavior.26
Addition of excess X– shifts this equilibrium to the left. This is clearly a fast equilibrium relative
to the timescale of the electrochemical measurement since we do not observe distinct waves that
may be assigned to Ru2(chp)4X and [Ru2(chp)4]+. These results indicate that both Ru2(chp)4X
species and free X– are chemically relevant on the timescale of photolysis experiments in fluid
solution at room temperature (vide infra).
Figure 4. Cyclic voltammograms of Ru25/4+ couple for 3-5 versus Fc/Fc+. E1/2 for each species is
marked with a dashed vertical line.
Table 2. E values for Ru25/4+ couple for 1-5 vs. Fc/Fc+ in CH2Cl2 with scan rate = 100 mV/s.
*
#
Electrolyte is 0.1 M. Indicates quasi-reversible. Previously reported against SCE26b and
converted here to be against Fc/Fc+.27 ‡Previously reported against Ag/AgCl28 and re-measured
here for direct comparison.
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Compound Electrolyte E1/2 (V) Ec (V) Ea (V)
–
-1.1#
–
–
1
2
3
4
4
5
5
NBu4PF6
NBu4PF6
-0.687
–
-0.525‡ -0.581 -0.469
NBu4NO3 -0.401* -0.465 -0.338
NBu4PF6
NBu4ClO4 -0.179* -0.230 -0.127
NBu4PF6
-0.145* -0.197 -0.094
-0.267* -0.388 -0.146
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Photolysis Screening by Mass Spectrometry. MALDI-TOF mass spectrometry is a
particularly useful method for screening photolytically-active compounds. In this case, the
MALDI-TOF nitrogen laser (337 nm) is the light source, and photolysis products can be directly
observed in the mass spectrum. The most prominent set of signals for 4 and 5 in MALDI-TOF
+
mass spectrometry experiments corresponds to the Ru2(chp)4 core with the characteristic Ru2
isotopic distribution centered around m/z = 717 amu (Figure 5 for 4; Figure S2 for 5), indicating
facile loss of the axially-bound oxyanions. In the case of 4, there is a weak Ru2 signal centered at
m/z = 733 amu, which is consistent with an [Ru2(chp)4O]+ ion, suggesting that an Ru2O species
could be formed upon photolysis of 4. This is also similar to the case of Ru2-azide compounds
that show Ru2N signals in their mass spectra due to photolysis.2 To further support this
18
–
18
hypothesis, we used labeled O-nitrate (N18O3 ) to form Ru2(chp)4 ON18O2 (4*), and we found
that the Ru2O feature shifts in the mass spectrum to m/z = 735 amu (Figure 5). This shift clearly
indicates that the axial O atom in the [Ru2(chp)4O]+ ion derives from nitrate and is fully
–

consistent with photo-dissociation of NO2 or NO2 from 4. The m/z = 733 amu feature is present
but barely discernable in the spectrum of 5 (Figure S2), suggesting to us that perchlorate may not
be as suitable a precursor for the formation of an Ru2O intermediate. Therefore only 4 was
investigated further.
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Figure 5. MALDI-TOF mass spectrum for 4 (black, top). Simulation (red) indicates isotope
pattern at m/z = 733 amu is due to [Ru2(chp)4O]+. Upon isotopic labeling, MALDI-TOF mass
spectrum for 4* (black, below) shifts by 2 units, as confirmed by simulation (red, bottom).
In photolysis experiments of 4 there are two possible sites at which bonds could break
homolytically: (a) the Ru–ONO2 bond or (b) the RuO–NO2 bond (Scheme 4). Previous studies
have indicated that either site is possible.11a,11b,29 Heterolytic RuO–NO2 bond cleavage is another
possible pathway (pathway c in Scheme 4), which has been demonstrated for perchlorate
compounds.11b Both pathways b and c would explain our mass spectrometry results. Upon
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
homolysis (pathway b), the resulting radical species NO2 should be EPR active, unlike its Ru2O
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counterpart Ru2(chp)4O (6), which is anticipated to have a ground state of S = 0.30 Heterolysis
(pathway c), on the other hand, would give rise to an EPR-active Ru2O+ species. Thus, we
decided to use EPR spectroscopy to assess the mechanism of photolysis for 4.
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Scheme 4. Possible products upon exposing nitrate complexes to photolytic conditions.
Photolysis of 4 in Frozen Solution at 77 K and in Fluid Solution at Room Temperature.
The EPR spectra of 2, 4, and 5 (Figures S3, 6, and S4, respectively) were measured at 10 or 15 K
in a frozen solution of CH2Cl2. Though electrochemical measurements (vide supra) suggest the
presence of an equilibrium between Ru2–bound and –unbound nitrate species, the 10 K EPR
spectrum of 4 can be modeled with a single axial signal, with effective g values of 3.86 and 1.95,
consistent with an S = 3/2 ground state where D >> hν (Table 3). Thus, the nitrate-bound 4 is
most likely the dominant species in solution at this temperature, and its prominent EPR signal
can be used to assess the efficacy of photolysis of 4 in frozen solution.
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Figure 6. EPR spectrum and simulation of 4 recorded at 10 K.
Table 3. EPR spectral simulations for 2, 4, and 5.
Compound
g
2
2.125
1.94
4
2.01
5
2.00
1.95
1.93
g
E/D
HStraina
0.006
850, 350,
450
0.035
1200, 900,
1200
0.033
1550, 850,
1100
a HStrain accounts for anisotropic line broadening due
to unresolved hyperfine coupling
Exposure of a frozen CH2Cl2 solution of 4 to 350 nm wavelength light at 77 K for 8 hours
yields no change in the intensity of the EPR signal of 4. Switching to 254 nm light and
photolyzing for 16 hours at 77 K yields the EPR spectrum shown in Figure 7. There is a slight
decrease in the signal intensity from the S = 3/2 signal of 4 and, more significantly, a new feature
in the g = 2 region is present. This new signal is an isotropic 1:1:1 triplet, clearly indicating a
radical species with hyperfine coupling involving an I = 1 14N nucleus, and it compares favorably
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to known literature values for NO2 versus those of NO3 (Figure 7, inset). The presence of
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NO2 suggests that, though photolysis of 4 proceeds in low yield at 77 K, homolytic cleavage of
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the O(5)–N(5) nitrate bond is the primary photolysis pathway (pathway b in Scheme 4).
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Figure 7. EPR spectrum of 4 in CH2Cl2 taken at 10 K after 16 hours of frozen photolysis using
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254 nm light. Inset: simulations of NO3 (blue, above) and NO2 (red, middle) compared to 4
after frozen photolysis (black, below).
In order to improve the yield of photolysis, subsequent experiments were performed on
fluid solutions of 4 in CH2Cl2 at room temperature under N2. Under these conditions, photolysis
is complete in a shorter time period of 4 hours using 350 nm wavelength light. Using the
isotopically-enhanced analog 4*, GC-MS analysis of the headspace of the reaction confirms
formation of N18O2 (m/z = 50) in significant quantities (Figure 8), further supporting the
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homolytic cleavage mechanism (pathway b in Scheme 3) suggested by our EPR results.
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Figure 8. GC-MS headspace analysis for the formation of N O2 (m/z = 50) after photolysis of
4* at room temperature under N2 for 4 hours using 350 nm wavelength light. As compared to the
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counts for m/z = 50 amu for the N2 control, N O2 is clearly formed under reaction conditions.
Oxygen Atom Transfer via Room Temperature Photolysis of 4. Room temperature fluid
solution photolytic experiments were also performed in the presence of an excess of the well-
known oxygen atom acceptor PPh3 and monitored for the formation of oxygen atom transfer
products. A CH2Cl2 solution of 4 and PPh3 (20 eq. vs. 4) was photolyzed for 4 hours using 350
nm light at room temperature under N2. Analysis by P{1H} NMR spectroscopy indicates the
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formation of the intermolecular oxygen atom transfer product OPPh3 in > 100% yield
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(determined by P NMR integration against a standard of PPh4Cl) (Figure 9). The identity of
this product was confirmed by doping with an authentic sample of OPPh3 (Figure S5) and is
further corroborated by ESI mass spectral data, which shows that the product formed in this
reaction with 4 has a mass of m/z = 279 amu (consistent with OPPh3) (Figure S6) and shifts by 2
mass units to m/z = 281 amu (consistent with 18OPPh3) upon using 4* (Figure S7).
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Figure 9. Yield of OPPh3 after exposure to different oxygen atom sources, both with and without
exposure to photolytic conditions.
The > 100% yield of OPPh3 implies that more than one active oxidant is formed under
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these conditions. As mentioned above, some amount of free NO3 is expected to be present based
on our electrochemistry results. Upon UV irradiation at ~ 300 nm, unbound nitrate is known to
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eliminate either P O or O– 32 or to isomerize to peroxynitrite.33 To test the possibility that
unbound nitrate is the sole oxygen atom source, photolysis of NBu4NO3 was performed under
identical conditions as previously expressed. OPPh3 is indeed generated but in less than one-third
the yield as when 4 was used (Figure 9). We also considered the possibility that the Ru2 complex
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could simply act as a photosensitizer for free NO3 . A control reaction was therefore performed
in which NBu4NO3 and PPh3 were photolyzed in the presence of Ru2(chp)4Cl (3) as a photo-
sensitizer (Figure 9). OPPh3 is generated in better yields here than without 3, but this result still
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does not match our findings with 4. Therefore, OPPh3 can be formed from free NO3 anion but is
formed more efficiently from 4.
It is conceivable that O2 could be formed from either nitrate photolysis or bimetallic
reductive coupling of Ru2O intermediates and could be the oxygen atom source for formation of
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OPPh3. To test this possibility, 4* was photolyzed in a CH2Cl2 solution at room temperature and
analysis of the reaction headspace was performed using GC-MS. These results indicate that 18O2
is not formed (Figure S8). Another potential oxygen atom source is the photolysis byproduct
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9b,10
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NO2 .
To probe this possibility, PPh3 was exposed to NO2 . ESI mass spectrometry data
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indicate that the resulting product is indeed OPPh3 (Figure S9). To see whether NO2 is fully
consumed under our reaction conditions, 4 was photolyzed in a CH2Cl2 solution containing 20
equivalents of PPh3 at room temperature, and analysis of the reaction headspace was performed
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using GC-MS (Figure S10). Free NO2 is still detected under these conditions, though in smaller
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yields than without PPh3 present. Thus NO2 is likely to be an oxygen atom source in this system
but clearly cannot be the sole source. We therefore propose that the oxygen atom transfer in this
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system derives from three active oxidants: free nitrate ion, NO2 , and an Ru–Ru=O intermediate,
giving yields of OPPh3 greater than 100%.
Finally, we were interested in determining the identity of the resulting Ru2 species after
completion of room temperature photolysis in the presence of PPh3. Only one Ru2 product was
observed and isolated. MALDI-TOF mass spectrometry and UV/Vis confirm this product to be
the precursor 3. This result was surprising to us since oxygen atom transfer from an Ru–Ru=O
species should yield an Ru2(II/II) product such as Ru2(chp)4PPh3, a species that we have recently
characterized.34 However, low-valent metal-metal bonded dimers are known to react with light
and halogenated solvents to yield one-electron oxidized compounds bearing an axial halide
ligand.35 This reaction sequence explains the formation of 3, as shown in Scheme 5. As
emphasized by Scheme 5, our results present a complete synthetic photocycle for oxygen atom
transfer from a photoactive oxyanion complex.
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Scheme 5. Proposed mechanistic scheme for the oxygen atom transfer reaction presented here.
Proposed intermediates 6 and Ru2(chp)4 are in dashed boxes.
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CONCLUSIONS.
Whereas the [Ru2(DPhF)4]+ core is not sterically accessible to bind non-linear anions as
ligands, the [Ru2(chp)4]+ core does support the formation of discrete, mono-oxyanion complexes
with η1-nitrate and -perchlorate anions. Mass spectrometry, EPR, and GC-MS analysis data
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suggest that photolysis of 4 proceeds to generate Ru–Ru=O species 6 and NO2 . Room
temperature photolysis of 4 allows for oxygen atom transfer to PPh3 to form OPPh3 in a synthetic
photocycle that regenerates 3. We therefore propose that PPh3 is directly oxidized by a
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combination of three active oxidants: photosensitized NO3 , reactive intermediate 6, and
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additionally by NO2 . This work demonstrates for the first time that the generation of a reactive
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metal oxo species from an oxyanion complex can be incorporated into a synthetic cycle. Further
exploitation of these reaction conditions, along with efforts to stabilize and characterize the
putative Ru–Ru=O intermediate are underway in our lab.
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EXPERIMENTAL SECTION.
General Methods. All syntheses were conducted under a dry N2 atmosphere using Schlenk line
techniques unless otherwise noted; product workup and isolation were achieved in air unless
otherwise noted. Dichloromethane (CH2Cl2) was dried with CaH2 and distilled before use.
Hexanes were obtained from a Vacuum Atmospheres Solvent System and degassed prior to use.
All materials were commercially available and used as received, unless otherwise noted.
Compounds 126b,36 and 32d,22 were prepared according to literature procedures. Photolysis of
frozen samples of 4 were performed in a Rayonet RPR-200 photochemical reactor with light
from 254 and 350 nm mercury vapor lamps.
[Ru2(DPhF)4][NO3] (2). Ru2(DPhF)4Cl (200 mg, 0.196 mmol, 1 eq.) was dissolved in CH2Cl2
and added to a suspension of AgNO3 (500 mg, 2.94 mmol, 15 eq.) in 3 mL of THF in air. The
color of the mixture changed from green to purple-blue almost instantaneously and was allowed
to continue stirring at RT overnight. The solids were filtered off and the remaining solution was
left to evaporate slowly to yield dark purple crystals of the product. Yield: 180 mg, 87.7%. MW:
1045.10 g mol-1. MALDI-TOF (m/z): ([M – NO3]+) 984. IR (ATR): 3053, 1773 [νsym NO3],
1591, 1520, 1486, 1449, 1364, 1349, 1314, 1214, 1175, 1156, 1078, 1027, 936, 827, 761, 693,
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668, 658, 619. UV-Vis (CH2Cl2):. λmax(ε) = 437 (4250), 527 (5950), 681 (7170 mol-1 L cm-1).
[C52H44N9O3Ru2CH2Cl22H2O]: calcd. C 54.59, H 4.32, N 10.81; found C 54.31, H 3.88, N
11.37. Crystals suitable for X-ray diffraction were grown via slow evaporation from a
concentrated solution of CH2Cl2 at room temperature.
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Ru2(chp)4ONO2 (4). Ru2(chp)4Cl (200.0 mg, 0.266 mmol, 1 eq.) and AgNO3 (54.6 mg, 0.321
mmol, 1.2 eq.) were dissolved in 30 mL of freshly distilled CH2Cl2 and allowed to stir for 96 h at
RT under static N2. A white precipitate (AgCl) formed. The reaction mixture was filtered
through a fine sintered glass frit. Excess CH2Cl2 was washed through the frit until it was no
longer colored. The filtrate was removed under reduced pressure, and the resulting purple solid
was washed with hexanes and collected. Yield: 195.5 mg, 94.4%. MW: 778.29 g mol-1. MALDI-
TOF (m/z): ([M – NO2]+) 733, ([M – ONO2]+) 717. IR (ATR): 3108, 2964, 1596, 1534, 1465,
1434, 1390, 1350, 1278 [νasym (ONO)], 1262, 1181, 1085, 1011, 964, 942, 931, 866, 795, 789,
724, 630 cm-1. UV-Vis (CH2Cl2): λmax(ε) = 532 (3890), 678 (1520 mol-1 L cm-1).
[C20H12Cl4N5O7Ru2]: calcd. C 30.86, H 1.55, N 8.99; found C 30.64, H 1.44, N 8.81. Crystals
suitable for X-ray diffraction were grown from a saturated CH2Cl2 solution at -80 °C.
Ru2(chp)4OClO3 (5). Ru2(chp)4Cl (200.0 mg, 0.266 mmol, 1 eq.) and AgClO4 (66.7 mg, 0.322
mmol, 1.2 eq.) were dissolved in 30 mL of freshly distilled CH2Cl2 and allowed to stir for 96 h at
RT under static N2. A white precipitate (AgCl) formed. The reaction mixture was filtered
through a fine sintered glass frit. Excess CH2Cl2 was washed through the frit until it was no
longer colored. The filtrate was concentrated under reduced pressure, and the resulting purple
solid was washed with hexanes and collected. Yield: 205.3 mg, 94.6%. MW: 815.74 g mol-1.
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MALDI-TOF (m/z): ([M – ClO3]+) 733, ([M – OClO3]+) 717. IR (ATR): 3107, 1596, 1536,
1433, 1391, 1337, 1263, 1154 [ν4], 1134 [ν4], 1075, 1025 [ν4], 1013, 932, 894 [ν2], 790, 723,
705, 668, 632, 610 cm-1. UV-Vis (CH2Cl2): λmax(ε) = 529 (2150), 666 (1310 mol-1 L cm-1).
[C20H12Cl5N4O8Ru2]: calcd. C 29.45, H 1.48, N 6.87; found C 29.20, H 1.68, N 6.26. Crystals
suitable for X-ray diffraction were grown from a saturated CH2Cl2 solution layered with hexanes
at room temperature. Safety warning: anhydrous metal perchlorate complexes are potentially
explosive.
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AgN18O3. 0.1 g HN18O3 (95 atom %, 65 weight % in H2 O), 0.1 g H2 O, Ag powder, and a stir
bar were added to a vial that was subsequently capped. This heterogeneous mixture was stirred at
50 °C in air for 48 hours; periodically the mixture was manually rotated and the solvent mixture
forced to the bottom of the vial as it had crept up the walls of the vial. A white solid became
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visible as the reaction reached completion, which was re-dissolved in the H2 O. The supernatant
liquid was then decanted away (using a pipette) from the heterogeneous solid mixture into a new
vial and allowed to evaporate to dryness, leaving a crystalline product, which was dried under
vacuum at 50 °C overnight. Yield: 126.8 mg (76.5%). IR (ATR): 1676, 1657 [νasym (18ON18O)],
1293 [νsym (18ON18O)], 792 [ν (N18O)], 694 cm-1.
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Ru2(chp)4 ON18O2 (4*). AgN18O3 was ground into fine powder and then used in an identical
procedure as 4. Yield: 141.2 mg, 67.7%. MW: 784.29 g mol-1. MALDI-TOF (m/z): ([M –
N18O2]+) 735. IR (ATR): 3108, 2964, 1596, 1534, 1465, 1434, 1390, 1350, 1253 [νasym
(18ON18O)], 1262, 1181, 1085, 1011, 942, 931, 866, 795, 789, 724, 630 cm-1.
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Solution-phase Reactions. A 0.5 mM CH2Cl2 solution of the nitrate source (4, 3 + NBu4NO3, or
NBu4NO3) with a 20-fold excess of PPh3 was prepared on a 30 mL scale in a quartz Schlenk tube
(flask “A”). A 10 mL aliquot was transferred to a different flask (flask “B”), which was wrapped
in foil, and allowed to stir under static N2 for 4 hours without exposure to photolytic conditions.
The remaining 20 mL solution was photolyzed in flask “A” under static vacuum at room
temperature using 350 nm light for 4 hours. After this time a 10 mL aliquot was removed and
transferred to a 25 mL Schlenk flask (flask “C”). Solutions in flasks “B” and “C” were reduced
to dryness under vacuum and analyzed by NMR with a known quantity (1 eq. based on 4) of
PPh4Cl for use as a comparative standard. 31P{1H} NMR (298 K, 400 MHz, CDCl3):  29
(OPPh3), 23 (PPh4Cl), –5.5 (PPh3).
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Physical Measurements. Matrix-assisted laser desorption/ionization (MALDI) time-of-flight
(TOF) mass spectrometry data were obtained using an anthracene matrix on a Bruker
ULTRAFLEX® III mass spectrometer equipped with a SmartBeam® laser in positive ion
detection mode. ESI mass spectrometry data was collected on a Thermo Q Exactive PlusTM mass
spectrometer and GC-MS data were collected on a Shimadzu GCMS-QP2010 Ultra
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spectrometer. H and 31P{1H} data were obtained using a Bruker Avance III 400 MHz
spectrometer. UV/Vis spectra were obtained using a StellarNet Miniature BLUE-wave UV-Vis
dip probe with a Tungsten-Krypton light source and a 10 mm path length tip. IR spectra were
taken on a Bruker Tensor 27 spectrometer using an ATR adapter (no matrix). Cyclic
voltammograms were taken on a BASi Potentiostat using Epsilon software in CH2Cl2 solutions
with 0.1 M electrolyte and 1.0 mM substrate. The electrodes were as follows: glassy carbon
(working), Pt wire (auxiliary) and Ag/Ag+ in CH3CN (reference). The potentials were referenced
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versus the ferrocene/ferrocenium redox couple by externally added ferrocene. Elemental analysis
was performed by Midwest Microlab, LLC in Indianapolis, IN, USA.
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EPR Spectroscopy. EPR data were acquired on a Bruker ELEXSYS E500 EPR spectrometer
equipped with a Varian E102 microwave bridge interfaced with a Linux system. An Oxford
Instruments ESR-900 continuous-flow helium flow cryostat and an Oxford Instruments 3120
temperature controller were used to control the sample temperature. A Hewlett-Packard 432A
power meter was used for microwave power calibration, with measurement conditions as
follows: for 2 – 9.3762 GHz, 4 G modulation amplitude, 2500 G center field, 5000 G sweep
width, 5.024 mW power, 55 dB gain, 327.68 ms time constant, 10 ms conversion time, and 15 K;
for 4 – 9.3765 GHz, 4 G modulation amplitude, 2500 G center field, 5000 G sweep width, 5.024
mW power, 60 dB gain, 655.36 ms time constant, 10 ms conversion time, and 10 K; for 4-
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hν/NO2 – 9.3765 GHz, 4 G modulation amplitude, 2500 G center field, 5000 G sweep width,
5.024 mW power, 60 dB gain, 655.36 ms time constant, 10 ms conversion time, and 10 K; for 5
– 9.3832 GHz, 4 G modulation amplitude, 2500 G center field, 5000 G sweep width, 5.024 mW
power, 55 dB gain, 655.36 ms time constant, 10 ms conversion time, and 10 K. Spectral
simulations were performed using the program EasySpin.37
X-ray Crystallographic Data Collection and Structure Determination. Crystallographic data
were measured at the Molecular Structure Laboratory of the Chemistry Department of the
University of Wisconsin–Madison. Suitable crystals of 4 and 5 were selected under oil and
ambient conditions. For 4, a purple block shaped crystal with dimensions 0.728 x 0.374 x 0.216
mm3 was selected, and for 5 a purple plate crystal with dimensions 0.166 x 0.155 x 0.094 mm3
was chosen. The crystals were attached to the tip of a MiTeGen MicroMount©, mounted in a
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stream of cold nitrogen at 100(1) K, and centered in the X-ray beam using a video monitoring
system. The crystal evaluation and data collection were performed on a Bruker Quazar SMART
APEX-II diffractometer with Mo-Kα (λ = 0.71073 ꢀ) radiation. The data were collected using a
routine to survey the reciprocal space to the extent of a full sphere to a resolution of 0.70 Å for 4
and 0.80 ꢀ for 5 and were indexed by the APEX program.38 The structures were solved via
direct methods and refined by iterative cycles of least-squares refinement on F2 followed by
difference Fourier synthesis. All hydrogen atoms were included in the final structure factor
calculation at idealized positions and were allowed to ride on the neighboring atoms with relative
isotropic displacement coefficients. Absorption corrections were based on a fitted function to the
empirical transmission surface as sampled by multiple equivalent measurements.39 The
systematic absences in the diffraction data were uniquely consistent with the space groups P21/c
for 4 and P21/n for 5, yielding chemically reasonable and computationally stable results of
refinement, and both structures were solved using direct methods using XS software.40
Compound 4 is a pseudo-merohedral twin with a twin component ratio of 54:46. The twin
components are related by a 180° rotation about [1 0 0]. Compound 5 is a non-merohedral twin
with a twin component ratio of 60:40. The twin components are related by 180° a rotation about
[0 0 1].
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ASSOCIATED CONTENT.
MALDI-MS and EPR spectra and simulations for 2 and 5; crystallographic data for 4 and
5, including tables for selected bond distances and angles; 31P{1H} NMR and ESI data for
formation of (18)OPPh3. The Supporting Information is available free of charge via the Internet at
http://pubs.acs.org.
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AUTHOR INFORMATION.
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Corresponding Author
*Email: berry@chem.wisc.edu
Current Address
‡ MTA Centre for Energy Research, Surface Chemistry, and Catalysis Department, PO
Box 49, H-1525 Budapest, Hungary.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGEMENTS.
We thank the U.S. Department of Energy, Chemical Sciences, Geosciences, and
Biosciences Division, Office of Basic Energy Sciences, Office of Science (DE-FG02-
10ER16204). A.R.C. thanks the National Science Foundation for a Graduate Research
Fellowship (DGE-0718123). NMR and EPR facilities at UW-Madison are supported by the NSF
(CHE-1048642 and CHE-0741901, respectively), and mass spectrometry instruments are funded
by NIH (1S10 OD020022-1 and NCRR 1S10RR024601-01). We thank Dr. Ilia Guzei for
crystallographic insights and Dr. Linghong Zhang for assistance with GC-MS measurements.
REFERENCES.
(1) (a) Yoon, T. P.; Ischay, M. A.; Du, J. Nat. Chem. 2010, 2, 527. (b) Prier, C. K.; Rankic, D.
A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
(2) (a) Pap, J. S.; DeBeer George, S.; Berry, J. F. Angew. Chem. Int. Ed. 2008, 47, 10102. (b)
Long, A. K. M.; Yu, R. P.; Timmer, G. H.; Berry, J. F. J. Am. Chem. Soc. 2010, 132, 12228. (c)
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agreement that the favored electronic ground state for 6 is the singlet state. See SI for
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