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Science Magazine 5824 2007-04-27
Science Magazine 5824 2007-04-27
a. entanglement disappears for
p~ OB = 1, which coresponds to finite time
‘This phenomenon his been called “entanglement
sudden death” (15) Because the concurrence of
the initial state (p = 0) is C= 2a8, the ex
tanglemont dynamics of to states with te same
be quite diffe
Photoas area usoful experimental tool for
emonsiraing these properties and, more gene
ally, for studing quantum channels Whe the
fone given in Eg. I, as the davoberance mech-
Figs 2. Boerimental setup. A
amplitude decay channel for a
single photonic qubt. Because of
the polarized beer spliter PBS1,
the H and V companentsof pola
‘zed photons respectively propagate
along countescodenise and dod-
Wise paths within the irterferome-
ter. Wit half-seve pate HNP set
at", they ave coterertly recom
bined ino the outgoing spatial
mode 0, which represen the
"acuum’ sate” of the reser
fer other angles of HWP, the V
‘component undegoes a rotate
conesponding tb its protebiisic B
“éecay" into the H component,
hier PBS serds to outgoing
mode b, representing the “one-
‘ciation sate” of the reer.
Wave plates HWP2 and OVIP2,
togyer with PBS2, are used for
tomography of the polarization
stale of outgoing modes @ and b,
which are recombine! fncaherenty
‘on PBS2 through HWP3 and are
sent to te same detedor. IF is an
imerference fier. (B) Ampituce
decay channel applied to entan-
sled qubits. The entangled states
‘generated by parametric down-
‘conversion in ype I neninear crystals.
2441.60
anions can be implemented ina contol mane
ne. Let us asociate the and polarizations of
photon, respectively, tothe ground and excited
sais ofthe Wvo-bve system S, The reservoir &
in tum is repaesemtal by ovo diffrent momen
tum modes of dh phovan,
Figure LA shows a Samnc-tke
ter that implements the amphtude-decay channel
| fra single qubit. A photon, nally in the
incoming par of mode a, sitio ks horizon
{Ufyand vertical (P) polarzation components by a
polarizing beam spliter PBS, Let us ignen
halewave plates HWPL and HIWPC momenta.
The Fpoluizaion component & reflected and
propagates through the interferometer the
clockwise direction, and, if unaired, reflects
through PBST info the outgoing pat of mode 4.
“Tae M-polaczation component is ansonited and
propagates. through the inerfometer the
‘ountewoekivse dnction and transmits dough
J ougoing pan of mex a (J7),
isallgned so thatthe two pats
are guialy separa, making it possible 0
manipube the Hand polarization components
independ.
To realize the amplinide decay given in
Fg. 1. we use HWWPL 10 roate the po
‘of the V component toos(20)1’) © sin(20)H1),
‘where O isthe angle oF HWP1. Suppose that an
incoming pon is Vepolarizsd, When this po
ton exits the interixemeter through PBSI. i is
transmitted into made A with probability
(20) and reflected into mode a with prob
nweco
Tomography
pam
inwniae Tomography}
aye!
cae
mwrsao
anu sciencemag.org,ability cos420). This
setbed by )a)— VT p) Pa) + yp.
Identitying the outgoing moves a and (hich
‘comsspond 19 ortiogonal spatial modes) as the
slates of the ascrvoie with ew and one excie
tation, respectively, tis operations auivalert to
that on the |e) state in Eg. 1. An incoming
Hepolari! photon is left untouched, cone
sponding to the fr! line in Ea. 1. This process
therefore wales dhe amphinsle decay channel
and is Mentical to the devay of a two-level
system: HalEvave plate HWPC vied a 0
used solely t9 match the lengths of the 10
‘pica pats. The path kanths are adjusel 9
that i HWPI is ovicmied at OF, the polarization
slate in mode a aller the interfenaneteris exacly
the same as the input stu, Photons in modes a
and fare thea dveted tothe same quantum sate
tomography (QST) system (75), composed of
quarter-wave plate QWP2, halE-vave plate
and polarizing beam spiter PBS2, and
4 single-photon detector
‘equips with a 1-en (fll with at half max
cn can ths be de
Concurrence
eees
&
2. Results for amplitude decay channel (A)
Experimental amplitude eccay for 3 single qubit.
AV) and Py(Vare the probable of detecting an
input Vpolaried photon in the V and H siaes,
respectively; PH) and Py(H) are the probabilities
for an input #-polaized photon. The points
‘correspond to experimenial data, and the lines are
linear fis, (B) Entanglement decay asa function of
the probability p. The squares coxespond to
‘experimentally obained values of A forthe case
Ip = ala. The slid line & the theoretical
predidion of the concurrence for this state, given
by Eq, 2; the cote tne shows the valu of , given
by Eq 3 The triangles are experimental values of A
forthe case I= lal? an the deshed ine is the
theoretical prediction for A and C, which are
equivalent for this state,
munscioncamag.org
mur) interference fier and a | Smmdiameter
aperture. Mode is recombined snccberently
‘with moxie a on PIS2 sta! bath odes can be
elect with a single detector This achioved
by assuring that the path Leng dilfeence be-
twvcen mods 4 and fis greater than the eoher=
‘nce kength of he photons, which i determined
by the with of the interference fers (0.1 men).
The half-wave plate HIWP3, aligned at 45°,
transforms H-poarized photos into (polarized
fonss, Bocuse PES2 wansmits Zpolarzation
and reflects F-poarization, the combination of
HAVPS and PBS2 reflects photons that were
originally f-polasized. This assures that the
QST performed is identical for both modes a
and f,
Using the intrrometer deserbed shove,
wwe staed both the decay of a single qubit and
the dynamics oF two entangled two-kvel ss
tems intemeting with independent amplitude-
decay rserois,In the experimental Sup (Fig
1B), polrzation-entangked photon pairs with
‘wavelength centersd around 884 nm were
produced usinga standard source (/9) composed
‘oF two aajacent type LilO, nonlinear erysals
pumped by 2441 G-nm continuous-wave He Ci
Taser. One crystal proiuces photon pars with
Fpelarizaton and the other produces pais with
HEpolatzation.. Aer propagation nk) spatial
smd filtering, the H and V modes are spatially
inistinguishabl, and a photon pai is deserved
bby the pure sate W)= a A181) |B expt) 1)
With high fidelity. half-wave plateanda quarer-
wave plate placed in she pump eam (Fig. 1B, At)
allow thecortol ofthe cosficiens o|and 8 and
the relative phase 8 ofthe ste (9.
“The dosay of a singe qubit was investigated
experimentally for box Hand H2polarized
pphotors by generating states 1”) and) 1) and
repstering coincidence com's, with one photon
propagating though the inerieromete and the
ther serving as a trigger. The coincidence
Aetovton Window (e = $s ~ 1S m) was longer
ten the path iflesense between outgoing modes
Purity
gge.
8
eae
e
Fig. 3. Puriy as a function of p for the
amplitude damping channel. The squares cer-
respond to experimentally obtained values of
the purity for the case Ip? = 3lal? the solid
line isthe theoretical prediction. The triangles
are experimental values of the purity for the
‘ase ipl? = lol, and the dashed tine is the
corresponding theoretical prediction.
REPOR
and Sen Figure 2A shows PA). Pull).
PYM )and Prd) asa tunstion ofp, whee PAA)
is the probably of fin 1 K-polwized
Photon i the J sate ater the interfere: The
leer behavior in is chuacteitc of exponetil
seeay in gif P= 1 eT.
For the investiztion of eatanglement dy-
nomics, normaximally entangled sites. were
prdduced and cach photon was sent o a separate
imerteorncter, which implement an armpits
damping reservoir, and then Wo a QST system.
The alf-save plas HWP and HWPS vere xt
to the same angle O, so thit the resem al
though indkpenvat, acted with the same proba
biliy p. QSTot ta t0-photon sate flloweatthe
teal recipe of 6 coincidence measuraments (8),
Each measurement lasted 90s, giving an aver
age of aboat 250 coincidence evens. We re
peated the same procedure for differen sales
‘of p, obtaining the tomographic reconstruction
fof the output two-photon polarization state in
all eases. The concurrence was calculated using
gs. 2and 3. in all figures horizontal enorbars
rprssertunceriainy in aligning the wave plat
and vertical eor ars correypand othe anda
eviaions of Monie Carlo samples obiained
fiom randomly generated counts Sllowing the
‘alstcs ofthe experimental da (20,
Figure 2B displays the concunence and the
‘quantity A, given by Eg, 3, a8 function of the
slay probebiliy Fr 060 tal states that. ak
‘hough not pute, are very chose to = aH
B ewyid) HT): stax [dona by |B?
Uiriangles), nd sine Ml, defined 6? = 30?
(squares). Tomography of the inal states 1
and H showed them to have the same concur
rence (08) and similar purity (-0.91 w 0.97)
“The theoretical curses were obisine by applying
Eq. 1 to the experimentally determined initial
ses. which carespond wo p= 0, Forni sate
|, entanglement disappears asymptotically, and
the concurence poes to zero enly witen beth n=
sinidualsyssems have davayed completely (p= 1
eg 2s
Coneunence / Pu
>
Fig. 4. Exoerinental rests for the dephasing
resenoit. Concurtence (Squares) and pytiy (Wien
‘ls) ae shown for the case fl? = 3. The solid
line the corresponding theoretical prediction for
‘concarence, given by Eq, 2. The dashed line te
‘theoretical prediction for purty, gen by tp, The
‘oncarrence goes to zero asymptotcaly
SCIENCE VOL316 27 APRIL 2007
sil
581i REPORTS
For ital sate I, however, the entanglement
Ihchaves voy lilerenly: Tae Concurence goes to
2ze10 for p< | hus demonsrating “entanglement
sudden death.” We stress that the onset of
scquabilty (C ~ 0) occas a the same point fr
all tanglemera quaiiers and is noe a panicle
aft ofthe concurene.
Ici also ihasenive wo stay the purity. de-
fincd as tp, asa funetion of the decay prob
ability (Fig) for sas Vand Mtn bl eases
the purity aches a minimum but is restored
‘when p~ when all phorors have “decayed”
to the Hpolarizaion ste, Ste I is mere
mixed thi state Fin the intermediate stages of
this procoss because it ass a lager 7) com
ponent and tas becomes mere entangled with
the environment
“To further illistate the usefulness of the
present scheme far stadying decoherence of
‘entangled systems, we performed a second es
periment surlying the phase-darmping channel,
desribed by the map (7)
1)5210)y—+ t)52 Oe
(¢s® 0) VI Peds O)e + VPleby@ le
iG)
This map could reproseetelastis seatering be
tween om and servo Sates e) ads) are
not changed by the tention, but sy coherent
superposition of then gets entangled with the
reservoir, Thre is no longer deeay, but only ks
‘of cobstense between ground and excited sates
‘The dephasing map can be iinplemenied with
the samo interferometer though the addition of
an extra IIWP a 43° ia mode b bet the O
system (or, equvaloth through the removal of
HIWP3 sand redefinition of the QST measure-
‘ments) For the dephasing channel, pve sates 1
and Il prseat identical bohavier, becoming
completely disertangket only wher p= 1
Figure 4 shows the concurrence (squares) and
bipacive purty (riangks) as a function of p for
the entangled sate I
{In demonstrating the sudden disapy
fof the entuiglement of a bipartite system, in
duced by the interaction with an envionment,
‘our results show that aril stles with the
sane inal concurrence may exhibit, for the
same reservoir, ithe an abrupt or an asymptote
isppearance of entanglement, even though the
onstucnts of the system afiays exhibic an
asymptotic decay. We hive explicitly shown
that this behavior also depends om the char=
acteristics of the reservoir through Iwo ox
amples corresponding fo amplitude decay and
dephasing. The experimental setup represents &
relible ant simple method for studying the c=
zmamics of entangled systems interacting with
ccontollad environments
References and Notes
1M Meben, Chan. Quertum Compton ed
(Quarta ofan Centre a Pe,
amb, 260,
2 eet OP vine, Mie 404,247
‘ca.
here, 6 sar, Proceso the
lxrntand Confrence on Carat Stan ond
Signe Pcs, Benga, Tai (IE, New Yo,
1960, pp. 175479
NC Gh, ys fer ee 67, 6 90.
Gi, ory itl HZ, Fe Mad
Phy 74, 145 COED,
6 CM tee et Phys Re Let 70,1895 (993,
2. Bevnmenter ea, Nate 390, 55 (1997.
8. .Bes 5. Banc, Den, Hy § Pops,
Py et 89,1124 990),
9. Dia Bia, Ge
‘3 oath
10, WI Zak, er ld Phys 75,725 200.
AL Lois Ine doom Dai, Een
1 Reais pring, Bet, 203, 9p. 157-16,
2.) Da) lve Phys Bs A69 052305 C0.
BB Ty J. Bay Pps. Lt. 93, 14644 (208)
1H, MF Sas Plime, L Dodo, M-Zage
Bee 473, O05 000,
35, Thu JH ey Pp Re Lt, 97, 140403 (2000.
16, WK ste, Phys fe et 80, 245 (998),
1D. Ram certguin tut nth he ition of
se 9 deat
le, we 434,
Pop Roe AGA, 083312 GOOD,
1. 7.6 Ha Wal, AG Wie, Apps,
P.M thar Py ee A, R773 GOP
201.8 Apt, Ree FG. fa indore
Amie Mole nd Ope Poy Seman Cin
Ee ir Sone, CX, 20552, 107-62,
21 SP Wit, FM'S be Davo Fe,
A thet, Mate 440, 20222005.
22 Seppe bythe Bran Fring ven
(PES, RON FU, nd FARE Ths wok war
perm 3 ut to Brain Mer vats
lee Guar herstn,
12 Janay 2007, acented 20 March 2007
odieaiace 1902
Enantioselective Organocatalysis
Using SOMO Activation
Teresa D. Beeson.*? Anthony Mastracchio,** Jur-Bae Hong,’*
Kate Ashton,** David WC. macitillan™?*
The asymmetric c-addtion ef relatively nonpolar hydrocarbon substrates, such as ally and aryl groups,
to aldehydes and ketones remains a largely unsolved problem in organic sythesis, deste the wide
potential uty of ditec routes to such products. We reasoned that well-established chiral amine
‘catalysis, which activates aldchydes toward elecrophile addition by enamine formation, could be
‘expanded to this important reaction lass by applying a single-etecton oxidant to create a transient
racical specs from the eramine. We demonstrated the concept of singly occupied molecular orbital
(ONO) activation witha highly selective cralplation of aldehydes, and we here present preBminary
‘results for enantioselective hetereatylations and cytiation/halogenation cascades,
vor he pst ur ats the copy
O: indie esynees Ceerneos
Mah eomioslcive ca fas
mained focal point for extensive research
cffonts in bot industrial and academic
‘ner Come for Gass. game of Chen,
Pirceon Uesty, Feo, A C8S88, USA. htsen ef
Cheristy and Chr. Enea, clfoms tue of
chet, Pasaca CK 91125, USA
ba conespanience soul be added, Era
disaeilaprnceon ed
582
27 APRIL 2007 VOL316 SCIENCE
During this time, thousands of asyinnetic cate
lic reactions have been invented (1), im ac-
son! with the increasing need for enaetionere
smadicinal agons and the rapid advancement of
the fill of asymmncre sya’, Mest calytic
cnantioinductive processes are derived ee a
sina number of long-esablished activation
‘modes. Activation modes such as Lewis cid
cata (2), e-bond insertion (3), bond inser
tion (4), om transfer catalysis (5), and bydro-
gen bonding catalysis (6) hve each spawned
counless asymmetic restion clases, thereby
ramatically expanding. the synthetic tolbox
available to researchers in the physical and bir
logical sciences. necessary objective, then
‘ore, for the continaed advancement ofthe fick!
‘of chemical synesis is the design and imple-
mentation of distinct eatalyie-activation modes
that cnable previously unknown transformations.
‘Over the past 8 years, our labora
boon involv in the development ofthe fed of
at eles on the
‘enantioselective transformations. As part of those
sacs, we introduced the concept of ina
sis (7) an enal or enone activation mode
that lowers the energy of the subsirate’s best
‘unoccupied molecular omit, filing eneioe
solsetive C-C and CN conjugate additions,
cyeluallions, hydiogenations. and Fried
Grats akylations (8). Simukanceusly, Batt
and List () on the concept
isis (Fig. 1), which raises the
ray ofthe highest occupied! molecular oil
(HOMO) in aldehydes and Ke
with a lange range of eloemophiles (0), These
two modes of catalyst activation (iminium and
enamine) have provid, in ttal, more dhan 60
ssymmetic methodologic over the past 7 years
anu sciencemag.org,Given the established capacity of examines
and iminium ions to rapidly imerconvet vin a
red process (onan has four x electrons and
iminium has two m electrons), we rovenlly ques-
tioned whether it might be possible 16
‘upt this equlibsium cherncaly and thereby’ to
access a rode of catlytie activities that esc
froniclly bisets cuamne and iminium forte
‘niemeatyae | [euninecauiyen | [ sowo enn
~ LUMO activation HOMO activation SOMO activation
wine |
“40
CN x o
OO
aie, 1
cae
Fig. 1. SOMO catalysis via single-electron oxidation of 2 tansiently formed enamine. LUMO,
lowest unoccupied molecular orbital R, an arbitrary organic substituent
Table 1. Representative SOMO catalysi
benzoyl Boe. tert-butyl carbamoyt:€t ethyl
Enantiosetective aldehyde wallylaton is shown. Bz,
an
9 " er e001 yy,
. as on
it 2a eT
mee
ioe, inion, (mmectaoae
a a
© Jute Jace | + duh, Jl,
BUG yield, 91% ce ae T2% yield, 57% ce w
> hate date
s Ae Aros
7% yd, 05% ce
m
“Texas peome ih aiiine @1=OCHSineD.
petomed wh een
munscioncamag.org
wo Alam re
nnn Te
‘id deed by gs ronsegegicantss — qReacioes
REPO!
tion, Move specifically. we hypothesized that a
‘one-slectron oxication of a transient enamine
species (Fig. 2A) should gensrte a thie-m
econ radical cation with a singly occupied
molecular orbital (SOMO) thats activated toward
range of enantioscleetve cali transforma
tions pot curently pesible with established ex
inlysis concep
From the outset, we idntiied thre key de-
sign elements tosubntite this prepess. Firs,
wwe roconized the mechani reainement at
an cquilrium population of enamine must
undergo selstve oxidation
nine catalyst, an alley subst, al an
nium ion precursor Theowtcal support foe
cd
9 ianzaton potential (Ps) of 1b
exybpytolidne (IP = 72 eV). pynolidine UP —
RS eV) ad butanal (IP = 9 eV)--data that
reveal the transient enamine component 10 be
sufficiently more suscepible t9 oxidation than
the accompanying reaction parwers (7, 12)
‘Second, we urvlerstond tha the widespread
application of SOMO catalysis would requiee
the ilersificaton of an amine caralyst tt could
_gencriclly enforce high levels of enantinsootao
in the coupling of de pivotal radical cation with
a sarety of rch nucleophiles. On the basis of
density functional theory (DFT) calalations
(U3, 11, wo proposed thatthe imiczotiinone
‘catalyst 1 (8) should selectively fora a SOMO-
activated cation, DFT-2, that projeets the
thrce-aeclecton system away from the bulky
ten-buty! group, while the radial-cemered
catbon selectively populats an E configuration
10 minimize nonboading interactions ‘with the
imidwolidinone ring (Fig, 2B). In terms of
cenantiofacil discrimination, the calculated
DFT2 siracture alo reveals thar the beryl
group on the catalyst sytem should effectively
shield the n° ee ofthe radical cation, leaving
the si face exposed for enantioselective bond
formation
‘Third, we knew thatthe inttinsic value of
this sctisation mode would be definal by is
‘epoxity to enable use enantioselective reac
tions. Radical cations show great potential in
this vein, because they akwady patiipats in
many noncatytic C-C, C-0, CN, C-S, and
(CX (where X is a halogen) bond formations
5-19). Our analysis reveals the auractive
prospect of applying asymmetric SOMO ital
ysis w important problems sich as direct and
‘enantioselective allybe allylation, enolation,
anlaton,
tion, oF
“To test this activation concept, we scketed
the ditt and enantioselective allie ally
tion of aldehydes as representative trans
(20, 21), We receunized that he accompanying
allylaion products have boxn established as
ienportam chiral syrbons in chemical syrthesis
3), Experimesull, this allylation protecol
twas firs! examined in dimetiony cane (DME)
solvent with oetanal,imidazolidinone catalyst
SCIENCE VOL316 27 APRIL 2007
ars if
the presence of
583i REP
584
ORTS
‘etic arumonium nitrate (CAN) a the stoichio-
metic oxidart, and allyinmethylsilane as the
SOMO nucleophile Cable 1) 24). Pelin
suas revealed the soccestl exscution of our
desizn ideas to provile (Ry?
‘xeellentIevels oF enanoinduct
conversion [Table 1, entry 1; 81°
enantiomeric excess (ce). Experimens
probed the scope of the aldehyde component
in this reaction are summarized in Table 1
centres | to 6. There appeans to be substantial
lttde in the serie demand of the ralicale
cation substituent (compare ents 1 and 5, with
the substitncat being hexyl venus eyelshexyb,
allowing accoss 10 a broad variety of 2alky!
substted-t-pontenals (75 19 81% yield. 9110
‘94% co}, Moreover, a sarily of chemical ne:
tional appear w be inert under these mild
“A ee
propanal
waonev
oxidative conditions, including obstins, heones,
esters, a carbamates (ens 210 4 and 6: 70
to 75% yiekl 87 to 95% cel
Adkitionaly, Table 1 reveals that a diverse
amay of reich olefinic silanes 25) will wadily
ppamtcpate as allylic alkylaing regerss i this
ialtic proocol frtrcs | and 7 19 1D), For
‘example, methyl. phenyl. and 2-ayl substituted
allylslnes «an be tolerated without losses in
action efficiency or enarioconerl (ons 710
9: 77 ta 88% yield, 810 91% ee). The elton:
Aeficer olen cilyl2-meshybvimsthy ils
acrylate ako functions ellectively as a
‘nuckophile w provide the conespondin
ated adduct in S1% yield and 90% eo (entry
10), This la’ resuk poovides circumstantial eve
dence for the generation and participation of a
radicabcation specics, given the capacity of
4500
\— esposes
Fig. 2. (A) Catalytic chemical steps leacing to formation of the SOmO-acthated intermediate. Me,
methyt: Ph, phen (B) DFT-calculated three cimersional structure of the enanto-iferentiated radical
‘ation. (©) Possible transformations arising fiom enantioselective owanocataytic SOMO cals.
. wees
drm GO We a
w me Sy NaHCO, 26m 56 eld
ke tee vanes
. tonebiea1
a om
Ri econ. OF ie eete
i roan (ol
air 0"
e CAN (2 equiv),
tu Xo Snot tie
ww g. kA
on Renae 0°
octanal ‘radical clock: Arecetone 65% yield OM
3. (A) Enantioselective u-heterceryation of aldehydes via SOMO catalysis. CAN, ceric am
moniam nitrate. (8) Enantioselective olefin cyclization via SOMO catalysts. THE, tetrahycrofuran. (©)
‘Mechanistic investigation to determine the intermediacy ofa radical ction versus a carbocation.
27 APRIL 2007 VOL316 SCIENCE
cy 2-(metiyirimety ily aerate to fane-
tion as a viable SOMO nucksophie on account
‘of the captsativeefixt (26), yet net asefctive=
ly as a HOMO muceopnile because of din
‘Sod x density atthe olin termi, The sease
‘of agynmestic ixlaction observed in all eases
(Table 1)is consistent with eletive en
fof he alle substrate wit te s face of the
SOMO-octivated species 2, in complete accont
‘with the eakulated stocture DIT.
‘A survey of reaction media for this organ
catalytic allylation has reveaked that va
selvenis may be used without a sub
in reaction efficiency, provided that water is
iden (27) ARough th use of
nial scleetivy, reaction rate,
and chemical yitd (29), a often be
used as at alcnative solvers without allation
fof the buk medium (25), Moreover, extended
reaction times do not lead product pimeri-
zation or the formation of o,cdialislakisiydes
‘oF aldehyde dimerization adducts
iii the antcipted broad scepe of
SOMO activation, we present preliminary
results for the eramtiowectve ahetcrearylation
ly, exposure of
tert-butyl cazamoyl pyiroke 10
n conditions enables Lom
ful evel of enanioneletiv=
joctaal and
four SOMO activa
arylation with us
ity and excellent yields. Moreover, we have
found that unsaiurated aldchydes rapidly
undergo. enan ation ith
trapping of an exogenous hale. As vealed
fn Fig. 318, activation of ci-6-nonenal with cue
SOMO prowccl in the presence of LiCl leads to
the formation of a stereochemically. dense
‘yelopentyl ring system with excellent stereo
control [85% yiekl, 210:1 dinsereomeric ratio
{ce 95% eo). This hater result again provides
circumstantial evidence for the generation and
pusticipation of « radial-cation
the popensiy of radicals w under
with unsetvated olefins
We have undertaken studiss 10 more
lively vestigate the parti
Ist process. Speci
addition experiments were perfonmed with the
Vinyl cyclopropane suite 3, an esttshed
radical clock that was designed by Newcomb
ef ol. (30) differnt between a
mediated pathways ant cationic mechanisms
(ig, 30). Addition of the activated aldchyde
intermediate to the oltin 3 occurs with sub
sequent session of the benylic cyclopropyl
ond ard! not the a-methoxy eyeleprpy bord
This result i in complete ccond with a rca
pata and nota cationic addition mechanism,
Might the substantial scope
of SOMO setivation for wsetl tsnsformations
in omni syuthesis, We ancipae a wide range
‘of applications for pharmaceaccally importer
‘compounds and internedites. Afr ou initial
subnission of tis work, a similar appa was
also applied to aldehyde c-onidation (3)
anu sciencemag.org,References and Notes
LEM eer A Plat 1 Yomamat, h
Comprenive Agree Cts ota, Be,
B99} 23
2-H Yamanet, Ed ei Acs Onan yee
Ie, New Yo 2000.
3. RH Cabtee The Orgnclc Chemisty te
Tiosin tos Mieplnersece Weboken Nee
2005,
4A Nor a Ameena ie Doi Sates
(werner, Men Yr, 3998, 123-173.
5 ja Ey in ea Asner Sie Ne
WHC Hen Yau eh 2 2600, cap 6
(6.5 Tair, EH Jose, Agen Che. hE 5,
1520 206),
7A A Avera C1 Ber, 0 eG Mac, JA
‘he So. 122,424) (200).
8G day 0. € Mac, Aichi, At 39,79
(en aed eons tere,
9,154 8A tees FB LAr, Chm, So
1, 2395 e010.
40, Lis, Chen Com 2806, 19 (2008 and
‘erences er
2 lr, redo Deere, He hin ets
eu 257 con.
12.01, Ein Harbook of es and Piss
(GRC fe Hem Yr. 78,2995 gp. 20-220
18. OF aadasons were peed a the
BRYMESTIAGaa NBL STG leech
‘ory ing Gurion 03 sole (04
1M. Me Tr et ay sie 09 str Cus,
alge, 208.
15 K taps, T Ott K Tonka, Mua Cher
tet tp) 92, 2059 0920,
2b Me ehgee See KR. Gps, JO
‘her 73,949 008.
1D. Ate. ser dn. ie. 5 122, 5616 200,
Be, | Sng 5. Bbd08, J Oo, An
(hem Soc 32, 1192 (2000.
19, Pts, Pb eb, dl Crane Ges
(We, Wek, cry, 20) vo 2,
pp 18-205,
23, Ogoroatsy ia cembiston wit ergonomic
Lalas tas revoutben applied We
aan: ayaton of hes
(ahem | A Cedoa, gen Pelt 5,
1952 20001
22.0 We MLL Gey, hem Ree 102, 29212008,
23 Seyden Pee in Ciel Aor ad gna in
Ammer Stes Wie letercec, Men ak,
99, 1395.
otra and mettre alate oy appertig ator
mma on Scene see
25, Medan we specdate fat aden the wich
tliane the veka sper resin the
leemoten of jaf raat wedges pid
silat teh caepodig BL eter re 8
Slaton wt cern lei famuton
26.1 ike Mey Z onus, Pe Ap. Ce.
6, 1635 G40.
27, Ne ineecion F195 equialet ef voters eq
te sce anh leo earn eee in mbt
‘avs 9, latte tanya ed
cn.
2
REPORTS I
2, Sch rode OME ws found cnin scent te
te vce opal ets The oi wt bye
Sie el gry ded OE es saianty er
‘emi yt
2, The eourtg of acon with liane wing sere a6
the bk mein previ heconepndg alton
Pod n 77s 05% conven ae 2 hh.
90 HOH Ue Toe Bint Nomen fem. Soe
Perkins, 2,867 (990,
31 MCP. SLM Hep Am. Chem, Se 129,395,
[rips ern 1 Ach 2007 10.84
issrzaen.
22 We Bark FA Pcl for inal sine in
peering Corson OFT easton ard. Fee or
utesu3e opeieertl contuten. areal agp
‘as ped by HD Moonta of Grrl
esta Snes get FOX 0782039198 sty
it rom Amgen, Mee ese abt ard he
Atel Furdsion USA TOE. fs ge fore rts
pedo tlertip, -8% i gael feo
Fosdotrat ell and KA 1 ghd ler a Meck
Imes peo! Slo
‘suppeting Onine Materat
secant 00.
Teter nd ate
20 Febay 2007, scape 20 March 2007
Nast onive 29 Hach 2907;
Indie th inline ing tis pope
A Dinuclear Ni(p-H)Ru Complex
Derived from H,
Seiji Oo. Ryota Kabe,?? Keiji Ushara,? Bunsho Kure)? Takashi Nishimura?
Saija C. Menon? Ryosuke Harada,? Shunichi Fukuzumi,® Yoshiki Higuehi?
Takashi Ohara,‘ Taro Tamade,* Ryota Kuroki*
odes ofthe active sien
Jydrogenase enzymes have proven challenging to prepare. We bolated a
paramagnetic dinuclear nicke-ruthenium complex with abridging hydro gad rom the heterotic
cleavage of Ha bya dinuclear NiRu aque comples in meter under ambient condions (20°C and
1 atmosphere pressure). The structure ofthe hexaccordinate Ni-H)Ru complex nas unequivocally
determined by neution difection analysis, and it comes dosest to an elfectve analog forthe core
‘stucture ofthe proposed active form of the enzyme.
ogee ae taal cars tat
H= te astm fn Wo
rns and wo deton ©9U
fdrogen atop © ‘periments ime
plicate asa first step the heterolytc elvavage
(0 toa prcton and a hydride ion (HP) (1-3).
Hydrogenases are classified inio. vo major
families on the basis of the metal content of
° cere for Future Chemisty, Rysta Univesity, Fukeoka
119-0595, Japan. “Departen: of Waceral and Ute so
free, Oven of Aovanced Scerce and Betechion,
‘iaivate Sheol Eeing. Osha Uris. Sear
(Orlerted Reser for cence ond Ted lapan
Science and Testadagy Agen (ID, Sit, Osa 565
(0871 Japan. Deparment Ue Scene Giada School
‘fe sence, Unies Hyogo. Ko, Kami, Hyo90
(76-1297, aan esearch Goup fr Mole al
Bo. Ocartun Bean Science Orecore Japan Ame
fretgy Agency, Tol, Batak! 319-1195, apa.
“To wba coespanence shoul be added, Ema
‘engmbannc habs ap
munscioncamag.org
their respective dinuclear active sites that is,
[FoFe}nydrogemases (4) and [NiFe}hydrogenssox
(5,6), Recor progress tovard the strates and
Function ofthe hydirgenases has boon pronide
by xray analysis, spectroscopic techniques,
methods, and model stds (7),
theoreti
Xuay enstillogrphic studies have shown
thatthe resting-tate core ructue of [NiFelhy-
rogenase from Destdforibvio giges sonssts of
fone nicks! aiom and one iron atom, which are
bridgsd by wo cystic thioktes and ene une
tied ligand (depicted as X in Fiz. 1) (2.5, 6)
‘The beiduing ligand X in the resting ste is
propesed to be an oxygen lisand such as U0,
OWL, oF OF (6), The we of metal atoms and
bridging S and X ligands inthe Hp elcavage has
0 Far been the Subject oF controversy (9).
Many synthetic modeling effons have been
devoted 0 clucidaring the cove simcture of the
active farm ofthe [NiFefiydigense such as prep-
aration of [NiRujcomplewes by Rauchivss and
‘others (9-15). Nilu-ShGi-HFespovisis one of
the candids forthe ative fon 5, 16 17)
However, PMQ-S)u-1D°M compleses [ohare
"XL group 10 metals (Ni Pl and Py and*M =
cup 8 meta (Fe, Ru, and Os) as models foe
the active fon of the [NiFelfiydogensse have
yet to be reported
re, we ropes the success isolation and
‘exysicl Sructure ofthe paramagnetic Nig DRU
complex (NPLATLO HAD Ruby GM) NOS)
H2KNOs)}. where L = MW limethy NN
bis2-mercapioethyD 1.3 propane, hich
wnesynthesized by nacion ofa dianyretic dia
clear NiRU aqua complex [(NH#L RUN
{0P-CMeg(NOs {NOx i in wate
under ambient conditions (20°C an 0.1 May
Fig.2)
"We obvsnal the highly watersokible Nik
agua comple [1}S0a) by reaction ofthe aeni>
tu ag complex [RUC CAAEg AHI OW ISO
Fig. 1. Core structure of the resting form of
IniFeinyérogenase from D. gigas, determined
by xray analysis. [Adapted from (61)
SCIENCE VOL316 27 APRIL 2007
585i REPORTS
586
Fig. 2. Formation of @
NiGeMRU complex ob-
tained from the reaction
cof a NiRu aqua complex
with diyarogen Ge)
‘ater under ambient con-
‘ons (20°C and 01 WPA
Fig. 3. Strctare of [21(NO,) as determined by
neutron diffraction analysis. The ellipsoids are
‘at open to revel the three principal axes and
ate drawn to include 302% probability density
Selected bond lenaths WA) and angles (ea)
Nit-Mt, 1859 = 0.007; Nit-O4, 2122 = 0.005;
Nin-St, 2389 » 0.010; Nii-S2, 2362 +
0.009; ‘Nit-N4, 2.139 + 0.003; Ni2-N2,
2117 + 0.004; Rut-H1, 1.476 = 0.008:
Rut-S1, 2375 + OOM; Rul-s2, 2388 + 0007;
Nit M-Ru, 102.47 + 0.083; Nit-52-Rud,
snd Nit-S2-Rut, 70.4 = 0.2
{13800} 25) with he nike comes (NLM)
(19) aqucus soliton (20), Complex [1 a8
characterized by nuclear magnetic resonance
(NMR) (Figs SI 0 S3) and itrared (IR) spo:
troscopy (liz. SA, as well as by clecrespray
mass ionization spectromoary (ESEMS) (figs SS
to $7) and xray phetockeimon spectroscopy
(XS) (ig. $8, Nand C). Maunstie suscep
ity measurements eonfirmed Unt the compl
was diamagnaic (Hig. SOA). The solids
sinicture of [1]? was characterized by xray
feat fom are exystal oF |1}OTs (aber
OT = CE,SOs), ebtained from an aqueous
solution of (1](OTDs. prepared by a anion
‘exchange [I]SO,) with NeOT in water ig
S10), A vaiety of aniens (uch = SO2.OT.
‘oF NO, ) were investigated with regard to their
ability t9 induce isoltion of Une complexes as
feysals (fig, St}, The Ni center of [1KOTDs
sits in the pocket ofthe ttradentate ligand in
4 square planar arangement (tig. SIO) The
Rul O1 (agus ligand) bond length is 2.15
Nil~O1 disnce i 2.888
0.003 A. (Furor
praramets ae piven in tab St anc 82.)
The dinuclear NiRu agua complex 1[NOs)e
was quintitaively obtained from anion ex
change of [1(S0,) in water at approximately
27 APRIL 2007 VOL316 SCIENCE
pH 7 (ig, S11), Hy (0.1 MPa) was bubbled
through the phosphate baller solution (pH 6.8)
of [1]EXO3)s at 25°C w gradually precipice
datk-red crystals of [2](NOy), which wore
isolated by filtration {34% isolated yield based
fon [1](NOs)a}- As the waction progressed
(vithout the addition of the phosphate butler)
the pi ofthe solution steadily decreased (irom
product. The 1,0 ligand of fAJ(NOs)2 may act
as.a bse jo leas HO (Hy = HO H
1,0") (22). We charoeterizod [2|(NO5) by IR.
lig, S12), ESEMS (ip. $13), XPS (fig SS, B
and D), NMR (fig, SId), electron spin r0-
znance (ESR) spectroscopy (fig. S15), and mag-
netic suscepibilty measurements (lig. SOB),
Darkred crystals of [2}¢NO%) btn from
the aqueous solution of [2(NOs) were chars
tevizad by x-my (fig. $16) as well as newton
itasion analysis, the later chosen for its
saitvty to hydiides (Fig. 3 an fg. S17). The
RuHt distance (1.676 + 008 A by neutron
Aifaction analysis) in toe NiGutDRu moiey of
[2}¢804) is substanilly shorer than the RUT
divances (averaging 1.755 A by neutron dif
fraction analysis) ip the Ruji-liRu moiety of
[2(1-Clh)aSiMey) Ru3(CO),(u-41 BE)
‘witha bulky mets inker (23). The Niatom
‘of [21'NO)) adopts a distrtal cetahadral cooed-
nation goomety withthe terademte ligand, one
agua ligand, and one hydtido ligand (Fig 3), The
bridging Hato is loser dhe Ruatom (Ru-HT
1,676 = (008 A, Ni H = L.880-© 0.007 Ap inte
Nily-lDRu moiety. The Ru-H unit may serve
a8 a two-clectron donot to the Ni unit through
the bridging H atom (24), muchas in M(y-10)B
complexes (where M is transition metal), in
‘whieh the B-IL unit acts asa two-alectzon donor
to M (25), Ih this coment, there aw three ex
amples of hesacoondinate Ni(u)B complexes
‘with Figands whose strctares have been de
termined by x-ray analysis (Ni ~ 183 to
1.98 A)(26-28), The Ni-S- Ruangles (70 7
(03° and 704° © 0.2) fr [2|'NOs ae substan
tially smaller ui the Ni-S-Rusngles(86.81°
0.04 and 87.20" = 0.05%) for [1](NOs}s. The
ture Ni-S-Ru angles allow such staxtal
ha ese daniclear compenss. The NioRa
ixanoe (2.739 +0008 A) of[2KNO}) is shore
than thst (3.1611 = 0.0006 A) of [IKOTT x. A
similar tendency has been observed in the
[NiFeliydeyomse: ie, extended say abscesion
finesinicure sues on the [NiFebiydrogersse
hhave shown thatthe NiFe distance in the active
2512: 0007 A, which isshorter than the
Nise divance (2.906
form (29),
A posiiveon FST mass spectrum of[2](NOs)
in 10 is consistent with the above formulation
ad diucleaiy (fig, $13). A prominent sznal at
2 mussdohnrge fatiy (2) of S432 [relative
intensity ~ 100% in the m= range fom 20 to
1000) fs a characteristic distribution of Soe
topomess that matches well withthe calculated
‘Snopic disrition for [240]. To contin,
the origin of the hydride ligand of [2(NO,), Wve
synthesized Delabeled [2}NOs) by reactin of
[H}NOs)p with Dy in HO for 10 min, En EST
mass spocta, the sigral at n/= $43.2 shifts to
S42 (fig S18), This result indicates thatthe
deuterium atom is incorporated into [2\(N03)
We have confimmed that thew is no HUD ex.
shange between Dp and H30 under the conde
tions of ths experiment (at pH 7109 in HO for
[our at 25°C at 0.1 MPa of D3) An IR spec-
trum of 2](N0y) in the region of 1000 t0 2000
‘nv shows pak shift from 1740 t0 1248 er
ater isopic substitution of H by Din the
hydrido ligand position, Magnctic sasoptibiity
0.014 Avi
resting
measurements of [2}(NOs) yield y= 8» 10
ectromunetic units (emu) mol! at 300K,
eomepooding 1 a magnetic moment of 232
BM. 'H NMR and ESR measuremonts sho
indicate poransygetsm in [2}NOy) The reason,
for paramagnetisn & explained on the bass of
the tansfonnation of the vickelD spin site
hetcen singlet (8 = 0) square plans of (1
and a tipkt (S~ 1) pscudo-oetahedral of 2)",
iggerod hy the coordination of Hand 11,0 10
the nickel fon Complex [2](NO) is one of fess
‘examples of stable parimagnet
‘omplenes (30) The binding e
{ix XPS of [2(NOs)nfieates hata Ni atom as
4 simibi charge (883.2 eV) to that of [I KOTD
1832.9 eV),
species.
Previous suis of dinuclear t
‘complexes with io bridging sulfico |
MG-ShM (vb Ru or lr), that activate
Histo give MijcS)a(j+H)M species have been
| However, in those reported
studies, the feactions have heen earied oat in
‘organic solvent such astoluene. We
agus lig Xig1-S)2Ru unit not only 0
sain water solubility butalso to ct asa base to
form the NiqeS),QrEDRu species in water,
because we assumed that the hyrogenases
require the X tigand (H30. OFF, oF OF in
resting state fo activate H in aqucous media in
the same manner of this study
References and Notes
1. Commack Hey Rabson, igen 2 2 Fa
learn fo Rar lag & are, tnd,
on,
2 Fey, Sacre ed Bandy (pager Yap, Bark
1990, 97-126
2. Shel Meh Bock, Bop Ace 1368, 367
ison,
4. fers WM arta, B.-L, LC See,
Seence 282, 1853 (0738),
5. A Vole a, More 373,50 (995)
anu sciencemag.org,A Weide J Am Chon So. 228, 2989,
986.
7, Speci ue n degen | ee, §. Be,
Ely Cid Chen Re 249, 1517-1690 200).
8M orp el JA, Chem, Se 424,261
(eat
9. MLA Ryo TB ouch, 5 Wis,
Organomet 22,139 2003.
10, C ewer, | Re, Cor Chem, Ao 249, 555,
(acs
ALD... Peet, Chom So, es 32,268
(oes.
AC Mar. Specs, Me Se, Coord hem
‘a 2192241055 2001
1B. MY urntou, Can} me, Cord Ohm.
ex 206207, 533 B00
A ZA. OM, 1 Tabu A Cem, Se. 127, 950
(ost!
15. We 2hu ea, roe No dead Se USA. 302, 18260
(ca
1 5 fees tol, Am Chem Soe 225,89 (2003,
17. MBean ase T Babe, Bs Friehe,
Wabi, hem Se, 125, 13075 (203.
18. de, 6, Mes, Aime, H Sees
G Stern, Ogananctlce 16, 107 (997
19, Gf Cag A Rama, 0. iy, Me), Maroney, og,
‘hem 29,479 (193).
20. jer bd method re abl ion
rater n Scene One
2L A.C Ont etek, ramones 17, 5867 (se
22.5. Oge,H Ml ¥ aarbe, A Chm Se 324,
5 on.
23. A Abe Jeg Chin, Ate 259,351 97,
24 MHL Deni Gu 5 Aone, Ween,
1D ut nrg. Gem 1996, 651 (1959.
25. 1) Hoo, fl, Gh. Be 77, 263 (977-
26 VL ang, G0 WH Pojmaren 24, 5952005,
27 WML Arey, Memes, 6. Dorr rer,
Few D Rabinovich nr Che 48, 573620,
24. R Gann eta, ig Chon. 42,1709 (2003.
BIZ Gate te Chom Soe. 18, 1255 190,
32. Meni Po, ecrt Advonces hips
hemi (er, hme, c3, 2000),
pete.
Ae Jai © Und 8, sts, 5. Wer
Am Ce See 126, 244 (OO,
a
REPO!
BERG ti J Plot TB Ruch, Am Chem
Soc 32, 886 2000.
238 his nc ns supped by ans in 417350027,
1926507, 1033661, an 1868017 (emir of
Conca Cot fom he Minty of an,
Care, ps cee, a Tsing, pa aod 9
Core even rota Scere and Tecneagy
ogo Ian Sure Cb ae Ut) by
It Gyaloyaphie fr 5101 a0, hove
been dees wth he GmbidgeCyalogaphi st
Cee rede vererce numbers CODE 62767
(era 67675 (ry, and 637331 eeten
‘Stace sey
Supporting Online Materat
someon rece,
Mera rd etc.
figs stasis
Tate St ond 52
belereres
12 Decenber 2006; weit 12 Moreh 2007
seuiebxerce est
Paleocene-Eocene Thermal
Maximum and the Opening of the
Northeast Atlantic
Michael Storey,? Robert A. Duncan? Carl C. Swisher 1?
‘The Paleocene-focene thezmal maximum (ETH) hes been atvibuted toa sudden release of carbon
dioxide andior methane. Nr?" age determinations show thatthe Danish Ash-17 deposi which
‘rer the PETM by about 450,000 years in te Alantic, end the Skieenteme Formation Tt
representing the end of 1 = 0.5 milion years of massive volcanism in East Greenland, are coeal. The
relative age of Danish Asb-17 thus places the PETIA onset after the beginning of masive flood basalt
volcanism at 56.1 + 0.4 milion years ago bit within error ofthe estimates continental breakup tine of
55.5 + 0.3 million years ago, marked by the eruption of mid-ocean ridge basalt-tike flows, These
‘orelations support the view thatthe PEIN was triggered by greenhouse gzs release during magia
interction wit basn-iling carbon rch secimentary rocks proximal to the embryonic plate boundary
between Greenland and Europe.
uring the Paeacene-Eocene the
Dimins it, ete ate
omperatrosehy $°C ihe ps2)
and more than °C in he Anti (2) 0 come
jnetion with ocean aciicaon (2) and the
calinction of 30 XP of doepsca bene
specks (9. The inet of he
tke yam bran: derese in the
rari ted brea be
mentary eatbon (4) hich i onsite. wth
the rapa ation of 1500 gists of
dephaed catbon, in the form of erbon den
fnilor matane, ito the hydosphere and
stoapher (7) The PET dught to have
lad only 210,00 to 220,000 scr with st
ofthe dscrese in SC accu owe 20000.
arpa at the bing ofthe evn (8
“quaternary Dig uboaten, Depwinent of Etennen,
Secry ae Spt ange, Rsk Unies Cente, Post
‘Offs Bo 260, 400 Pek, Denmark. “Calge of Oceanic
ard feragheic Sire Orson Sate Unves, Canalis
‘0897S, USA. ‘Deine of Gece See ages
Unive, Paar, 6854 68, US.
munscioncamag.org
A possible tigasr for the initiation of the
PETM is a peti of intense flood haat miag-
‘mutism atending the opening of the Noah Atlan-
tie (9, 10), by generaizng metamoephic methane
fiom sil fxrusion into basin-tiling eason-sich
sedimentary weks (I! Here we present ®AC"Ar
correlation of
Eauly Tentiary voleanic rocks of East Greenland
and the Facrae Islands withthe Danis Ash-I7
deposit, which clescly overies PETM sequences
in th Noth Athan. by Fast Greenland 2 >S-km
thick sequence of plateau bats formed in 1.0
(05 millon yeas (My). A surge in mega pro-
duction, couplet with the eryption of mid-ocean
tg basalt (ORB) ke flows in te ker pat
‘ofthe lod has sequence, idcates the initiation
of seafloor sycading «$85 = 3,
ago (May, The onset of the PETM ccnmcates
closely it this eakup-hied magmatisnn
“The Non AaieTasous Province (NAP)
includss the basic and pic Ivas of Bafa
Island and West Groeabnt: the
dominantly tholitic kwva flow saqacaces of
stick,
the Blessevile Kyst of East Greenland; the
scwwantipping reooers of the Greenland and
nothvest European voleanic ified margins the
Fave [ands and British Tertiary haste las
and the aseisnic ridgos contesting Island to
cither margin of the cental Nenbeast Atlanic
1), The tol area of the NAIP is 3 > 10°
‘hu? (22) andi volume is estimated tobe $10"
kan? to 10 10 kin (12-14), The East Groen
‘BlosevilleKys0 and Fact Ishin hod bss
‘opposite ends of the Groenland-Loekext-
"Ac age detrminations show that pre-
‘akup vekeanieacivity in East Greenkand and
the Facroes began at ~61 Ma (15-17), Soven
lava flows cover the duration of mag
RTS i
‘CS ($00,000 years) inthe uppermest pat of
the Facross loner series LS), indicating a very
lew eruption rate by $7 Ma (I8) (Fig, 2), The
FLS extends into eaves C24 as the lava fhe
innmaitey below the capping -0-aick coal
hearing sediment horizon (9) is weversely mae
rized (78). The vokanic hiatus 2 represented
‘on the Fastocs. afer the cad ofthe inital phase of
volcanism, has an estimated duration of 6
(04 My Fi. 2, In East Greenland, volcaniclastic
sediments veri the ELS equivalent, the Nansen
Fjord Fomatioa (27), hich inchs Inhaes that
onain coal iaysments sw plant impsins 20,
Alter the period of litle or no voleanism,
oad basal euptens commenced on a massive
scale in East Grogan ang the Facroes (Fig 2).
Flood basalt activity ia East Grocnland is 6
resented by four regionally extensive forma
tions with a combined suatigraphicthikness of
>S km. The Milne Land Foamation (MLF). the
‘okies ofthese four formations, inclades MORB-
like lowTi hasaks balay up the succession
(20) that provide comeation with the Facrocs
mide serics (FMS) an upper series (FUS) [Fi
2}, Palcomagnetic data saest a hich cruption
SCIENCE VOL316 27 APRIL 2007
587i REPORTS
Fig. 1. Map of the
North’ felantic region
shewrng the distibation
of igneous rocks related
to the NAIP and DSO
site 550, where Danish
AsbI7 closely overlies
the PET. 24, seatoor
magnetic anomaly 247;
BK Blossevle Kyst GC
Gardiner Complex: MAR,
rate at the onset ofthe FMS (18). In the MLE.
East Greenland lavas show a regula decrease i
the Dy/Vb ratio up through the section, india:
tive ofa progressive drop inthe mean pressure of
patil meting (22) andcensistnt with sing and
Shining of the lithosphere. A PAD Ar age