Hydrogen Peroxide Complex of Zinc

Article abstract of DOI:10.1021/jacs.5b10450

Metal(H₂O₂) complexes have been implicated in kinetic and computational studies but have never been observed. Accordingly, H₂O₂ has been described as a very weak ligand. We report the first metal(H₂O<

Full text of DOI:10.1021/jacs.5b10450

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Communication
A Hydrogen Peroxide Complex of Zinc
Christian M. Wallen, John Bacsa, and Christopher C. Scarborough
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b10450 • Publication Date (Web): 11 Nov 2015
Downloaded from http://pubs.acs.org on November 13, 2015
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A Hydrogen Peroxide Complex of Zinc
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Christian M. Wallen, John Bacsa, and Christopher C. Scarborough*
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Emory University, Department of Chemistry, 1515 Dickey Drive, Atlanta, GA 30322, U.S.A.
Supporting Information Placeholder
8
lar hydrogen bonding involving bound H O . Herein,
ABSTRACT: Metal(H O ) complexes have been impliꢀ
2
2
2
2
cated in kinetic and computational studies but have nevꢀ
er been observed. Accordingly, H O has been described
we report the first coordination compound of H
O
2
2
, a
II
Zn (H O ) species that features hydrogen bonding beꢀ
2
2
2
2
as a very weak ligand. We report the first metal(H O )
tween bound H
O
2
2
and the ancillary ligand.
2
2
adduct, which is made possible by incorporating intraꢀ
molecular hydrogenꢀbonding interactions with bound
II
H O . This Zn (H O ) complex decays in solution by a
2
2
2
2
secondꢀorder process that is slow enough to enable charꢀ
acterization of this species by Xꢀray crystallography.
This report speaks to the intermediacy of metal(H O )
2
2
adducts in chemistry and biology, and opens the door to
exploration of these species in oxidation catalysis.
Hydrogen peroxide is a readily accessible and “green”
1
oxidant, with major industrial applications including
III
Figure 1. (a) Proposed Fe (H O ) adduct in cytochromes
P450. (b) Shaik’s computed Fe (H O ) adduct demonꢀ
strating the importance of secondꢀsphere hydrogenꢀbonding
interactions with bound H O for preventing “uncoupling.”
2
2
bleaching of raw cotton and wood pulp, textile bleachꢀ
5
III
2
3
2
2
ing, and propylene epoxidation. These industrial proꢀ
cesses are improved by the use of metal catalysts that
activate H O . Remarkably, metal(H O ) adducts that
7
2
2
2
2
2
2
(
c) Demonstration by Mayer that H O is a very poor ligꢀ
2 2
III 6a
may be important intermediates in H O activation have
2
2
and for Ga .
never been observed, although they have been kineticalꢀ
4
III
Ligands that engage in secondꢀsphere hydrogen bondꢀ
ing have been utilized extensively by Borovik, with
highlights including the sole report of a highꢀspin
ly implicated. In cytochromes P450, an Fe (H O ) adꢀ
2
2
duct may be the “second oxidant” or a precursor to the
second oxidant (Figure 1a), and is likely the source of
III
5
Fe (oxo) species stabilized by intramolecular hydrogenꢀ
free H O formed via “uncoupling.” The intermediacy
2
2
9
II
III
bond donors and O activation at Co centers that was
2
of Fe (H O ) complexes in cytochromes P450 has been
2
2
dependent on the presence and number of secondꢀsphere
contentious, and Mayer demonstrated that related (porꢀ
1
0
III
hydrogenꢀbond donors. Recognizing the higher acidity
of H O compared to H O and the corresponding
phyrin)Ga complexes do not interact with H O in anꢀ
2
2
2
2
2
hydrous CH Cl solutions despite the availability of
2
2
III
demonstration by Prikhodchenko that H O is a more
effective hydrogenꢀbond donor than H O, we targeted
2
2
open coordination sites on Ga and a strong interaction
11
III
6
2
between Ga and added H O (Figure 1c). However, a
2
ligands that would provide secondꢀsphere hydrogenꢀ
bond acceptors. We were particularly attracted by trianꢀ
ionic trisulfonamido derivatives of tren (tren = tris(2ꢀ
aminoethyl)amine) that have been demonstrated by Boꢀ
rovik to provide an electronꢀrich coordination environꢀ
recent computational study by Shaik supported H O
2
2
coordination in cytochromes P450, not as the “second
oxidant” but as an alternative route to the reactive
IV
7
Fe (oxo) species (Compound 1, Figure 1a), where hyꢀ
drogen bonding between the coordinated H O ligand
2
2
ment well suited for hydrogen bonding with H O and
2
and the surrounding environment was critical to the acꢀ
–
12
III
HO ligands. Reasoning that diamagnetic metals would
cessibility and longevity of this Fe (H O ) species (Figꢀ
2
2
1
enable the study of metal(H O ) interactions by H NMR
spectroscopy, we targeted Zn complexes supported by
trisulfonamido derivatives of tren.
2
2
ure 1b). Related computational studies of M/H O oxidaꢀ
2
2
II
tion catalysts (M = Mn, Os) also implicate the intermeꢀ
diacy of M(H O ) adducts that benefit from intramolecuꢀ
2
2
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Figure 2. Xꢀray crystal structures of the anions in 1-OH (left), 1-N H (middle), and 1-NH OH (right), highlighting intraꢀ
molecular hydrogen bonding. Aryl groups truncated for clarity.
2
2
4
2
Scheme 1. Synthesis of compounds examined. Yields
of crystalline products shown.
five other metal–(NH
2
OH) species that have been crysꢀ
1
3
tallographically characterized.
We next turned to exploring coordination of H O to
2
2
II
Zn . We found that H O can be readily extracted from
2
2
solid H O ꢀurea into anhydrous d ꢀTHF to provide up to
2
2
8
5
00 mM H O solutions with <5% H O relative to H O .
2 2 2 2 2
Addition of this solution of H O (1 equivalent) to a d ꢀ
2
2
8
THF solution of 1-H O resulted in a 0.72 ppm upfield
2
shift of bound water towards the freeꢀH O resonance of
2
2
.54 ppm with concomitant 0.05 ppm downfield shift of
the H O resonance away from free H O (9.40 ppm)
2
2
2
2
(
Figure S8). This was the first indication that H O inꢀ
2 2
teracts with 1-OH and reveals that K for H O disꢀ
2
eq
2
placement by H O is less than unity (Scheme 1). This
2
2
contrasts the observation that both N H and NH OH
2
4
2
quantitatively displace H O from 1-OH , and is conꢀ
2
2
sistent with H O being the weakest ligand of this series.
2
2
Encouraged by the interaction of H O with 1-OH in
2
2
2
d ꢀTHF, we turned to dehydration of 1-OH to probe
8
2
coordination of H O to 1 in the absence of H O. Forꢀ
2
2
2
mation of anhydrous 1 was accomplished by heating 1-
OH in glyme to 80 ºC overnight in the presence of 4Å
2
molecular sieves, followed by precipitation with penꢀ
tane. Dehydration was verified by the disappearance of
1
any resonance associated with bound or free H O by H
2
NMR spectroscopy. Addition of one equivalent of anhyꢀ
Combining H Ts tren, KH, and ZnCl in DMF, folꢀ
drous H
field shift of the H
with interaction between H
2
O
2
to 1 in d
8
ꢀTHF resulted in a 0.45 ppm downꢀ
proton resonances, consistent
and 1 to form 1-H O ,
2 2
3
3
2
lowed by addition of [nBu N][Br] and H O, provides
O
2 2
4
2
II
access to [nBu N][(Ts tren)Zn (OH )] in 92% crystalꢀ
O
2
2
4
3
2
line yield (1-OH , Scheme 1). Xꢀray crystallographic
although the nature of the interaction (coordination, hyꢀ
drogen bonding, electrostatic interaction) could not be
established from these data (Figure 3). Importantly, no
2
characterization of 1-OH shows hydrogenꢀbonding inꢀ
2
teractions between the bound H O protons and the sulꢀ
2
fonyl oxygens (Figure 2) similar to what Borovik obꢀ
interaction between H
and ZnCl in d ꢀTHF is observed by H NMR
spectroscopy (Table S1). The H proton resonance in
1-H shifts linearly downfield with decreasing temꢀ
perature with a slope that is steeper than that of free
or that of bound H O in 1-OH (Figure S7). This
large temperature dependence is indicative of strong
O and H Ts tren or between
2 2 3 3
1
12
served with other metals. Displacement of water from
-OH was readily accomplished with both hydrazine
H
2
O
2
2
8
1
O
2 2
2
and hydroxylamine, which are structurally analogous to
O
2 2
H O (Scheme 1). The Xꢀray crystal structures of 1-
2
2
N H and 1-NH OH also exhibit secondꢀsphere hydroꢀ
H
2
O
2
2
2
2
4
2
gen bonding interactions, in these cases demonstrating
hydrogen bonding with the terminal ZH group (Figure
2). While crystallographically characterized metal–
(N H ) complexes are abundant, we are aware of only
1
4
intramolecular hydrogen bonding in 1-H O .
2 2
2
4
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"
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H O
2
2$
*"
1
–H O
2
2$
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1$
*
"
1–OH2$
1
0
9
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δ(ppm)
3
2
1
1
Figure 3. From top to bottom, H NMR spectra (d ꢀTHF)
of H O , 1-H O , 1, and 1-OH . Free (top) and bound H O
second from top) and bound H O positions (bottom) are
2
marked with an asterisk. Free H O in d ꢀTHF appears at
8
2
2
2
2
2
2
2
(
2
8
2
.54 ppm.
1
-H O decomposes in solution to 1-OH by a second
order pathway (k = 3.8 × 10
cipitation of 1-H O resulted in a 1:1 mixture of 1-OH
2
2
2
–3
–1 –1
M
s , Figure S3). Preꢀ
Figure 4. TGA traces of crystalline 1-OH (top), powdered
2
1-OH (middle), and powdered 1:1 mixture of 1-H O and
2
2
2
2
2
2
and 1-H O in the solid state. This solid was explored by
1-OH
2
(bottom). Mass loss experimental/theoretical:
(top), 0.67mg/0.63mg (middle),
.70mg/0.82mg (bottom).
2
2
thermogravimetric analysis (TGA) to probe the strength
0.74mg/0.82mg
0
of the H O interaction with 1 in the solid state by comꢀ
2
2
parison to crystalline and powdered samples of 1-OH2
(Figure 4). These data show that H O is the first ligand
to be lost upon heating solid samples of 1-OH /1-H O
because there is a lowerꢀtemperature massꢀloss event
than observed in powdered samples of 1-OH . Thereꢀ
fore, in both the solid state and in solution, H O is a
weaker ligand than H O for 1.
2
2
2
2
2
2
2
2
2
Encouraged by the isolation of solid samples containꢀ
ing 1-H O despite the bimolecular decay pathway of
2
2
this species, we explored whether crystalline samples of
-H O could be obtained. Rapid crystallization of 1-
H O from THF with MTBE provided crystals with varꢀ
ying amounts of bound H O and H O , with the best
crystal examined having a 50:50 disorder of 1-H O
Figure 5) and 1-H O , each refined as a distinct comꢀ
ponent. The H O and H O ligands share the same apical
position. The electron density of 1-OH /1-H O (see
Supporting Information) unambiguously establishes the
presence of a bent H O ligand coordinated to Zn . 1-
H O is the first structurally characterized H O coordiꢀ
nation compound. H O coordination to Zn is analoꢀ
gous to coordination of N H and NH OH, where intraꢀ
molecular hydrogen bonding between both H O protons
and the sulfonyl oxygens is observed in the solid state.
The Zn–O bond lengths of 1-OH2 and 1-H O
2.185(10) Å and 2.171(10) Å, respectively) fall within
1
2
2
2
2
2
2
2
2
2
(
2 2
2
2
2
2
2
2
Figure 5. Xꢀray crystal structure of the anion in 1-H O2
2
from a 1:1 crystal of 1-OH :1-H O . Aryl groups truncated
2
2
2
II
2
2
for clarity.
2
2
2
2
II
While H O has been described as a very poor
2
2
2
2
6
a,15
ligand,
H O is a common ligand in coordination
2
2
4
2
chemistry. Both of these ligands can engage in hydrogen
bonding, so we probed the extent to which coordination
2
2
of H O to 1 was favored over coordination of H O . As
2
2
2
2
2
described above, addition of one equivalent of H O to
2
2
(
1
1-OH in d ꢀTHF results in a 0.05 ppm downfield shift
2
8
σ of one another, consistent with formation of a direct
Zn–O bond in each case. The O–O bond length in 1-
H O is 1.445(14) Å, indicative of an O–O single bond.
of H O from its uncoordinated position with a concomiꢀ
2
2
tant 0.72 ppm upfield shift of H O from its coordinated
2
2
2
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(
4) (a) Mirza, S. A.; Bocquet, B.; Robyr, C.; Thomi, S.; Williams,
position (Figure S8), enabling us to measure the equilibꢀ
1
2
3
4
5
6
7
8
9
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
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6
A. F. Inorg. Chem. 1996, 35, 1332ꢀ1337. (b) Wolak, M.; van Eldik,
R. Chem. Eur. J. 2007, 13, 4873ꢀ4883. (c) Theodoridis, A.; Maigut,
J.; Puchta, R.; Kudrik, E. V.; van Eldik, R. Inorg. Chem. 2008, 47,
2994ꢀ3013. (d) Afanasiev, P.; Kudrik, E. V.; Millet, J.ꢀM. M.;
Bouchu, D.; Sorokin, A. B. Dalton Trans. 2011, 40, 701ꢀ710.
rium constant for H O vs. H O coordination to 1 by
2
2
2
comparing these exchangeꢀaveraged chemical shifts to
their corresponding free and bound shifts (see Supportꢀ
ing Information for details; exchange of H O and H O
2
2
2
(
5) (a) Coon, M. J. Annu. Rev. Pharmacol. Toxicol. 2005, 45, 1ꢀ25.
is fast on the NMR timescale even at –100 ºC, Figure
(b) Denisov, I. G.; Makris, T. M.; Sligar, S. G.; Schlichting, I. Chem.
Rev. 2005, 105, 2253ꢀ2278. (c) Shaik, S.; Kumar, D.; de Visser, S. P.;
Altun, A.; Thiel, W. Chem. Rev. 2005, 105, 2279ꢀ2328. (d) Ortiz de
Montellano, P. R., Cytochrome P450: Structure, Mechanism, and
Biochemistry. Kluwer/Plenum: New York, 2005.
(6) (a) DiPasquale, A. G.; Mayer, J. M. J. Am. Chem. Soc. 2008,
130, 1812ꢀ1813. (b) Lithium oxalate monoperhydrate may contain an
interaction between lithium ions and the oxygens of hydrogen
peroxide in the solid state: Pedersen, B. F. Acta Chem. Scand. 1969,
23, 1871ꢀ1877.
(7) Wang, B.; Li, C.; Dubey, K. D.; Shaik, S. J. Am. Chem. Soc.
015, 137, 7379ꢀ7390.
(8) (a) Kwong, H.ꢀK.; Lo, P.ꢀK.; Lau, K.ꢀC.; Lau, T.ꢀC. Chem.
Commun. 2011, 47, 4273ꢀ4275. (b) Ma, L.; Pan, Y.; Man, W.ꢀL.;
Kwong, H.ꢀK.; Lam, W. W. Y.; Chen, G.; Lau, K.ꢀC.; Lau, T.ꢀC. J.
Am. Chem. Soc. 2014, 136, 7680ꢀ7687. (c) Chen, M.; Pan, Y.;
Kwong, H.ꢀK.; Zeng, R. J.; Lau, K.ꢀC.; Lau, T.ꢀC. Chem. Commun.
S4). We calculate that K = 37 (ꢁGº = –2.1 kcal/mol) in
eq
favor of H O coordination to 1 over H O .
2
2
2
ꢃꢄ– ꢅꢆ ꢈꢃꢆ ꢅ ꢈ
ꢃꢄ– ꢆ ꢅ ꢈꢃꢆ ꢅꢈ
ꢇ ꢇ ꢇ
ꢇ
ꢇ
ꢇ
ꢀꢁꢂ
=
≈ 37
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
H O remains a better ligand than H O even with supꢀ
2
2
2
porting ligands that facilitate secondꢀsphere hydrogenꢀ
bonding interactions, but the preference is not particularꢀ
ly stark: the ratio of bound H O to bound H O at equal
2
2
2
2
concentrations of these two species and 1 is ~6:1.
We have demonstrated the first H O coordination
2
2
complex, where the M–(H O ) interaction is facilitated
2
2
by secondꢀsphere hydrogenꢀbonding interactions. Coorꢀ
dination of H O speaks to the viability of metal(H O )
2
2
2
2
2
015, 51, 13686ꢀ13689.
9) MacBeth, C. E.; Golombek, A. P.; Young, V. G.; Yang, C.;
Kuczera, K.; Hendrich, M. P.; Borovik, A. S. Science 2000, 289, 938ꢀ
41.
10) Lucas, R. L.; Zart, M. K.; Murkerjee, J.; Sorrell, T. N.;
4,8
adducts as intermediates in catalysis, particularly in
reference to the “second oxidant” in cytochromes
P450. Furthermore, an understanding of how to faciliꢀ
tate formation of metal(H O ) adducts opens a new
(
5
,7
9
(
2
2
Powell, D. R.; Borovik, A. S. J. Am. Chem. Soc. 2006, 128, 15476ꢀ
15489.
pathway for exploring H O activation for substrate oxiꢀ
2
2
dation reactions, a goal that we are currently pursuing.
(11) (a) Wolanov, Y.; Shurki, A.; Prikhodchenko, P. V.;
Tripolskaya, T. A.; Novotortsev, V. M.; Pedahzur, R.; Lev, O. Dalton
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ASSOCIATED CONTENT
Supporting Information.
Synthesis and characterization of compounds, experimental
details, description of TGA and equilibrium calculations,
and crystallographic information. The Supporting Inforꢀ
mation is available free of charge on the ACS Publications
website.
(
12) (a) Park, Y. J.; Ziller, J. W.; Borovik, A. S. J. Am. Chem. Soc.
2011, 133, 9258ꢀ9261. (b) Lacy, D. C.; Park, Y. J.; Ziller, J. W.;
Yano, J.; Borovik, A. S. J. Am. Chem. Soc. 2012, 134, 17526ꢀ17535.
(c) Park, Y. J.; Cook, S. A.; Sickerman, N. S.; Sano, Y.; Ziller, J. W.;
Borovik, A. S. Chem. Sci. 2013, 4, 717ꢀ726. (d) Sano, Y.; Weitz, A.
C.; Ziller, J. W.; Hendrich, M. P.; Borovik, A. S. Inorg. Chem. 2013,
52, 10229ꢀ10231. (e) Sickerman, N. S.; Henry, R. M.; Ziller, J. W.;
Borovik, A. S. Polyhedron 2013, 58, 65ꢀ70. (f) Cook, S. A.; Ziller, J.
W.; Borovik, A. S. Inorg. Chem. 2014, 53, 11029ꢀ11035. (g)
Sickerman, N. S.; Peterson, S. M.; Ziller, J. W.; Borovik, A. S. Chem.
Commun. 2014, 50, 2515ꢀ2517. (h) Lau, N.; Ziller, J. W.; Borovik, A.
S. Polyhedron 2015, 85, 777ꢀ782.
AUTHOR INFORMATION
Corresponding Author
*C. C. Scarborough. Email: scarborough@emory.edu
ACKNOWLEDGMENT
This research was made possible through support from the
American Chemical Society Petroleum Research Fund
(53254ꢀDNI3), the National Science Foundation (CHEꢀ
1455211), and Emory University.
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