R ES E A RC H

INORGANIC CHEMISTRY in transition metal complexes (33, 34) and was

also the bonding motif that we observed in the
boron-based fixation of N2. Indeed, the reduction
The reductive coupling of dinitrogen of [(CAAC)BBr2Dur] by KC8 under an atmosphere
of N2 affords {[(CAAC)DurB]2(m2-N2)}, putatively
through the generation of the reactive borylene
[(CAAC)BDur]. Neither the likely monoborylene
Marc-André Légaré1,2*, Maximilian Rang1,2*, Guillaume Bélanger-Chabot1,2†, intermediate [(CAAC)BDur(N2)] nor any other
Julia I. Schweizer3†, Ivo Krummenacher1,2, Rüdiger Bertermann1,2, coordination modes were observed under these
Merle Arrowsmith1,2, Max C. Holthausen 3, Holger Braunschweig1,2‡ conditions. We were therefore interested in
studying the possibility of stabilizing such
intermediates by disfavoring the formation
The coupling of two or more molecules of dinitrogen (N2) occurs naturally under the of end-on m2-bridging complexes by increasing
radiative conditions present in the ionosphere and may be achieved synthetically under the steric repulsion of the ancillary groups at
ultrahigh pressure or plasma conditions. However, the comparatively low N–N single-bond the boron centers.
enthalpy generally renders the catenation of the strongly triple-bonded N2 diatomic To this end, we synthesized the dihaloborane
unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, precursor [(CAAC)BCl2Tip] (Tip, 2,4,6-triisopro-
we report the surprising organoboron-mediated catenation of two N2 molecules under pylphenyl) using standard methods and suc-
near-ambient conditions to form a complex in which a [N4]2– chain bridges two boron centers. cessfully reduced it in good yields to the stable
The reaction entails reductive coupling of two hypovalent-boron-bound N2 units in a single [(CAAC)BClTip]• radical (1), which is a one-
step. Both this complex and a derivative protonated at both ends of the chain were electron reduction step away from the hypo-
characterized crystallographically.

Downloaded from http://science.sciencemag.org/ on March 21, 2019

thetical base-stabilized borylene [(CAAC)

T
he propensity of carbon to form molecular
chains is unrivalled across the periodic
table. In stark contrast, chain formation
is heavily disfavored for nitrogen—the next
element on the periodic table. With its dis-
proportionately strong homonuclear triple bond
(as compared with N–N single and double bonds),
dinitrogen (N2) is the thermodynamic end point
of nitrogen chemistry (1). Catenated nitrogen
compounds tend to be metastable with respect
to decomposition and release of N2, rendering
them high-energy-density materials with appli-
cations in gas-generating formulations for air-
bag technologies, propulsion, and explosives (2).
Recent work has demonstrated the existence of
different phases of nitrogen at ultrahigh pressures
(3–6), ultimately leading to the identification of
the crystalline allotrope Nn, which consists of a
covalently bonded network of nitrogen atoms in
a cubic gauche structure (7). Further computa-
tional and experimental studies have identified
phases of catenated nitrogen in alloys with other
elements at ultrahigh pressures and often high
temperatures (8–10). Additionally, under plasma
conditions (11–13) and in the Earth’s ionosphere
(14), N4+, N5+, N5–, and other ions can be formed
from N2, processes that have no parallels under
ambient conditions (15). More recently, the de-
tection of neutral tetranitrogen (N4) from the re-
ionization of N4+, with lifetimes on the order of
microseconds, has attracted considerable atten-
tion (16, 17).
In synthetic chemistry, in which extreme tem-
perature and pressure conditions are usually un-
1
Institute for Inorganic Chemistry, Julius-Maximilians-Universität
Würzburg, Am Hubland, 97074 Würzburg, Germany. 2Institute
for Sustainable Chemistry and Catalysis with Boron, Julius-
Maximilians-Universität Würzburg, Am Hubland, 97074
Würzburg, Germany. 3Institute of Inorganic and Analytical
Chemistry, Goethe-University, Max-von-Laue-Straße, 7,
60438 Frankfurt am Main, Germany.
*These authors contributed equally to this work. †These authors
contributed equally to this work.
‡Corresponding author. Email: h.braunschweig@uni-wuerzburg.de
feasible, the chemistry of nitrogen catenae is
dominated by molecular species, with N2 once
again being both the start and end point of all
nitrogen-containing molecules. Indeed, the near-
totality of anthropogenic and biological nitrogen
chemistry arises from the initial transition-metal
mediated cleavage and reduction of N2 to am-
monia (18) and ends with the regeneration of
N2 through the denitrification of nitrogen pro-
ducts (19). Remarkably, even those compounds
that contain longer chains of nitrogen atoms that
are generally only kinetically stable, being en-
ergetic materials and prone to loss of N2 (20, 21),
are produced from NH3, which is generated from
N2 cleavage (Fig. 1). This is true of commer-
cially relevant products (1)—such as hydrazine
and azides—of transition metal–stabilized nitro-
gen chains (22), and of metal-free cyclic and
linear polynitrogen compounds (21, 23, 24–28).
To this day, the formation of nitrogen chains
directly from N2 remains elusive under ambi-
ent conditions.
Natural and anthropogenic reactions of N2
are generally transition metal–mediated. We
have recently demonstrated, however, that hy-
povalent boron species are capable of binding
and reducing N2 in the absence of transition
metals (29). The coordination and functionaliza-
tion of N2 by the transient dicoordinate-borylene
[(CAAC)BDur] [CAAC, 1-(2,6-diisopropylphenyl)-
3,3,5,5-tetramethylpyrrolidin-2-ylidene; Dur,
2,3,5,6-tetramethylphenyl] (30) was facilitated
by boron-to-N2 p-backbonding, which is usu-
ally the preserve of transition metal chem-
istry (31) but was enabled in this case by the
electron-rich, hypovalent nature of the borylene
center (32). Here, we report a surprising exten-
sion of this work, in which borylene chemistry
transcends transition metal mimickry by medi-
ating the spontaneous catenation of two N2
molecules into an N4 chain, capped by two
boron centers, under near-ambient conditions.
The end-on bridging (m2) coordination mode
of N2 between two metal centers is very common
BTip] (2-Tip) (35). Further reduction of 1 by
KC8 in toluene under argon affords the C–H
activation product 3, likely from the intra-
molecular insertion of transient borylene 2-Tip
into a C–H bond of the CAAC ligand. This pro-
cess has precedent with other CAAC-stabilized
arylborylenes, and its regioselectivity is con-
sistent with previous reports (29–31). The for-
mation of 3 thus strongly supports the formation
of the transient borylene 2-Tip from the re-
duction of 1.
When we reduced 1 using KC8 (10 equivalents)
in toluene under 4 atm of N2, we obtained a
turquoise-colored solution after filtration. In
this reaction, from a paramagnetic, 11B nu-
clear magnetic resonance (NMR)–silent reac-
tant (1), we obtained a diamagnetic product
featuring a broad 11B NMR resonance at d =
27.9 parts per million (ppm) (5). After we iso-
lated this product as dark blue crystals in a
moderate yield (31%), analysis of the mother
liquor revealed that it still contained 5 as the
main product, which we were not able to
further separate from the small amounts of 3
present as a contaminant. The conversion of
1 to 5 thus appears to be selective, but its
quantitative isolation from the minor side-
product remains difficult. The isolation of
crystalline 5 allowed us to elucidate its solid-
state structure by means of x-ray diffraction
analysis, revealing an unusual bonding motif
for nitrogen (Fig. 2). Instead of featuring N2
in the common end-on bridging motif, 5 is
best described as a bis-borylene complex of a
[N4K2] moiety, {[(CAAC)TipB]2(m2-N4K2)}, which
arises from the direct catenation of two N2
molecules mediated by the hypovalent boron
centers. The room-temperature 1H NMR spec-
trum of 5 showed broad resonances. At low
temperature, however, a sharpening of the
signals allowed us to discern spectra consistent
with a centrosymmetric molecule. Although the
line-broadening could be attributed to fluxional
processes such as hindered rotations in the
bulky substituents, no decoalescence of the

Légaré et al., Science 363, 1329–1332 (2019) 15 March 2019 1 of 4

R ES E A RC H | R E PO R T
Fig. 1. Schematic representation of the current commercial preparation of common nitrogen compounds via NH3 production,
versus the direct catenation of N2 reported here.
resonances was observed at temperatures as
low as –70°C, at which the signals are con-
siderably sharper. This broadening could
possibly be attributed to the influence of a
triplet excited state, which is consistent with
computational studies that predict a low singlet-
triplet gap.
Similarly, the solid-state structure of 5 reveals
a centrosymmetric complex in which the (NCB)
N4(BCN) core is entirely planar, suggesting ex-
tensive p delocalization. This conclusion is con-
firmed by the bond lengths within this planar
core, which are all indicative of partial double
bonds. The B–N bond lengths 1.442(2) Å, where the
number in parentheses is the estimated standard
deviation on the last digit of the measurement sug-
gest a degree of multiple bonding between boron
and nitrogen and lie between those in the pre-
viously described N2 complexes {[(CAAC)DurB]2
(m2-N2)} [1.423(4) and 1.403(5) Å] and {[(CAAC)
DurB]2(m2-N2K2)} [1.484(4) Å] (29). The short B–
CAAC bonds [1.526(3) Å] suggest B-to-CAAC back-
bonding typical of borylene complexes (29–34).
All the N–N bond distances in the N4K2 moiety of
5 are similar [1.349(2) Å for N1-N2 and N3-N4 and
1.335(2) Å for N2-N3] and lie between the ranges
of N–N double and single bonds {as exemplified
by azobenzene [d(N=N); 1.247(2) Å] (36) and 1,2-
diphenylhydrazine [d(N–N); 1.394(7) Å]} (37),
further confirming the delocalized nature of the
bonding in 5.
The dipotassium complex 5 is strongly basic
and could be selectively protonated. Upon addi-
tion of an excess of degassed water to a turquoise
toluene solution of 5, the mixture immediately
turned dark blue. The resulting product was 11B
NMR–silent, but protonation could be easily con-
firmed with the appearance of a sharp N–H vi-
brational band in the infrared spectrum (3315 cm–1).
Through subsequent filtration and slow evapo-
ration, we successfully isolated dark blue crystals
of {[(CAAC)TipB]2(m2-N4H2)} (6) in good yield
(75%). Contrary to 5, 6 displays paramagnetic
behavior at room temperature, which can be
attributed to a diradical structure. Variable-
temperature electron paramagnetic resonance
(EPR) spectroscopy of a toluene solution of 6
showed a dependence of the EPR signal intensity
on the temperature. Measurements in the 230 to
Légaré et al., Science 363, 1329–1332 (2019) 15 March 2019
290 K range are consistent with a thermally excited
triplet state for 6, and the results can be fitted to
a small singlet-triplet gap of 0.5 kcal mol–1 according
to the Bleaney-Bowers equation (supplementary
materials).
Single-crystal x-ray diffraction analysis of
6 showed that the tetrazene core is preserved
but that the structural parameters substan-
tially differ from those of 5, as would be
expected from its paramagnetic nature. The
B–N bonds [1.432(2) Å] are closer in length
to those of formal, covalent single bonds. Ad-
ditionally, the terminal N–N bond lengths lie
within the range of single bonds [1.371(1) Å],
and a conventional double bond exists be-
tween the central N2 and N3 atoms [1.272(2) Å].
This localized bonding motif is reminiscent
of known organic tetrazenes and of the pa-
rent N4H4, which possess central double bonds
in their most stable isomers (24, 38). Rela-
tively short B–CAAC bonds [1.534(2) Å], as
well as coplanarity between the CAAC p
frameworks and the trigonal planar boron
atoms, were also found in 6, these features
being in accord with known B–CAAC radicals
(29, 32, 35).
Using the same methods described above with
15
N2 as a substrate, the 15N isotopologues of 5
and 6 (5-15N and 6-15N, respectively) could be
prepared. In both cases, high-resolution mass
spectrometry (HRMS) analysis was consistent
with the quantitative enrichment of 5 and 6.
In the case of 5-15N, 1H- and 11B-decoupled 15N
(15N{1H,11B}) NMR spectroscopy gives two sym-
metrical multiplets at d = 13.2 and 69.3 ppm of
equal intensity, which is consistent with a sym-
metrical N4 chain. The multiplicity of the reso-
nances is consistent with an AA′XX′ spin system,
and the 15N–15N spin-spin coupling was con-
firmed with a 15N,15N{11B} correlation spec-
troscopy experiment. Thus, the preparation
and characterization of 5-15N and 6-15N not
only confirm the identification of a N4 unit in
5 and 6 but also provide a simple entry into
isotopically labeled 15N4 chains—which are
otherwise difficult to obtain—directly from the
coupling of 15N2 gas.
Despite the apparent differences of 5 and 6
in terms of magnetism and bonding detailed
above, a quantum-chemical assessment revealed
far-reaching similarities between both species. In
both cases, the computed strong delocalization
Downloaded from http://science.sciencemag.org/ on March 21, 2019
throughout the p-orbital framework is consistent
with the crystallographic bond distances. Fur-
thermore, the electronic structures of both sys-
tems are dominated by strong, nondynamic
correlation effects arising from small highest
occupied molecular orbital/lowest unoccupied
molecular orbital (HOMO/LUMO) energy gaps
(detailed discussion of the bonding situation is
provided in the supplementary materials). State-
averaged CASSCF(2,2)/DLPNO-NEVPT2/def2-
TZVPP calculations based on closed-shell singlet
M06L-D3/6-311G(d,p) geometries of 5 and 6 re-
sulted in antiferromagnetically coupled bira-
dicaloid (singlet) ground states, which lie
3.5 kcal mol–1 and 0.9 kcal mol–1 below the cor-
responding triplet biradicals, respectively. These
values are in agreement with the variable-
temperature NMR (VT-NMR) characterization of
5 (significant line-broadening at room temper-
ature) and with the VT-EPR results for 6 (singlet
ground state favored by 0.5 kcal mol–1), as well as
its paramagnetic character at room temperature.
The larger singlet-triplet gap computed for 5 is
consistent with a drastically lower thermal pop-
ulation of the triplet state, which provides a con-
vincing rationale for the relatively well-resolved
NMR spectra of this biradicaloid species.
The strong p delocalization in 6 is reflected
in the computed Wiberg bond index (WBI) pat-
tern and atomic charges resulting from natural
population analysis (NPA) (supplementary mate-
rials). With reference to the neutral constituents,
the NPA reveals a net electron transfer of 0.39 e–
from each borylene fragment onto the central
N4H2 moiety. A WBI of 1.66 indicates a central
N=N double bond, whereas significantly smaller
values were calculated for the terminal N–N
bonds (1.15), closely resembling the data ob-
tained for the parent tetrazene H2N–N=N–NH2
(N=N, 1.81; N–N, 1.11). Compared with the bare
borylene [(CAAC)BTip] (2-Tip), the B–CAAC
double-bond character in 6 is more delocalized
across the N–C–B groups, which also carry most
of the biradical spin density (fig. S7). These re-
sults suggest the Lewis structure representation
shown in Fig. 2, illustrating the p bond pattern
2 of 4
R ES E A RC H | R E PO R T

in 6. The bonding situation in 5 is similar, yet p

delocalization is even more pronounced, result-
ing in a weaker central N=N bond (1.31), which
is consistent with a smaller computed net elec-
tron transfer of 0.18 e– onto the N4K2 fragment
(supplementary materials).
We propose that the formation of 5 proceeds
through the initial coordination of N2 to the
transient borylene [(CAAC)BTip] (2-Tip) to form
a 1:1 borylene-N2 adduct (4-Tip). An analogous
intermediate without steric protection (4-Dur)
was postulated as an intermediate in the pre-
viously described end-on coordination of N2 to
[(CAAC)BDur]. Whereas in the case of the less
bulky 4-Dur the reaction with a second equiv-
alent of borylene 2-Dur is rapid (k1-Dur > k2-Dur)
(Fig. 3), the corresponding process is considera-
bly hindered by steric repulsion in the case of the
bulkier 4-Tip. Under these conditions, the re-
duction of 4-Tip by excess KC8 can become the
predominant mechanism, leading to a nitrene-

Downloaded from http://science.sciencemag.org/ on March 21, 2019

like radical, which readily dimerizes to 5 (k2-Tip >
k1-Tip) (Fig. 3). This last step is supported by pre-
cedent in the reductive dimerization of organic
azides (39) and diazo compounds (40) mediated
by a magnesium(I) reducing agent.
Whereas borylenes have been shown to bind
N2 in a manner akin to transition metals, form-
ing end-on bridging (and potentially also ter-
minal) N2 complexes, they retain a distinct
main-group character to their reactivity, as high-
lighted by the transformation of intermediate
4-Tip, which is more reminiscent of the re-
ductive coupling of organic diazo compounds
(40). Terminal N2 complexes of transition metals
are not known to catenate N2, even under reduc-
tive conditions, presumably because reduction
preferentially occurs at the metal center rather
than at the N2 ligand. These results underscore
Fig. 2. Reactivity of 1 with KC8 and N2 toward the catenation of nitrogen, including the solid-
the potential of low-valent main group elements
state structures of 3, 5, and 6, in which hydrogen atoms are omitted for clarity.
to unlock distinct reactivity pathways.

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ACKN OWLED GMEN TS
We warmly thank R. D. Dewhurst for the concept of Fig. 1,
K. Hammond and M. Müller for the synthesis of CAAC
precursors, and C. Mahler for mass spectrometry. Quantum-
chemical calculations were performed at the Center for
Scientific Computing (CSC) Frankfurt on the FUCHS and
LOEWE-CSC high-performance computer clusters.
Funding: Financial support from the Deutsche
Forschungsgemeinschaft is gratefully acknowledged.
M.-A.L. thanks the Natural Sciences and Engineering Research
Council of Canada for a postdoctoral fellowship. G.B.-C.
thanks the Alexander von Humboldt Foundation for a
postdoctoral fellowship. Author contributions: Experiments
were designed by M.-A.L. and performed by M.R., M.-A.L.,
and G.B.-C. Data analysis was done by M.-A.L., G.B.-C.,
and M.R. X-ray crystallography was performed by G.B.-C. and
M.A. The EPR investigation was led by I.K., and the NMR
experiments were designed by R.B. Computational
investigations were performed by J.I.S. and led by M.C.H. The
project was overseen by H.B. and coordinated by M.-A.L.
Competing interests: The authors declare no competing
interests. Data and materials availability: Experimental
and computational details, as well as NMR, HRMS,
ultraviolet-visible, and infrared spectroscopy data are
available as supplementary materials, and crystallographic
data are available free of charge from the Cambridge
Crystallographic Data Centre under reference numbers
CCDC 1876961–1876969.
SUPPLEMENTARY MATERIALS
www.sciencemag.org/content/363/6433/1329/suppl/DC1
Materials and Methods
Figs. S1 to S57
Tables S1 to S7
References (41–71)
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5 November 2018; accepted 15 February 2019
10.1126/science.aav9593
4 of 4
The reductive coupling of dinitrogen
Marc-André Légaré, Maximilian Rang, Guillaume Bélanger-Chabot, Julia I. Schweizer, Ivo Krummenacher, Rüdiger
Bertermann, Merle Arrowsmith, Max C. Holthausen and Holger Braunschweig

Science 363 (6433), 1329-1332.

DOI: 10.1126/science.aav9593

Boron brings nitrogen together

Whereas carbon is prone to making chains, nitrogen usually sticks to itself just once in the particularly stable form
of N 2. Légaré et al. now show that boron can coax two N2 molecules together under reductive conditions below room
temperature. Two borylene units sandwiched the resulting N 4 chain between them.

Downloaded from http://science.sciencemag.org/ on March 21, 2019

Science, this issue p. 1329

ARTICLE TOOLS http://science.sciencemag.org/content/363/6433/1329

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