A Mononuclear Nonheme Iron(V)-Imido Complex

Article abstract of DOI:10.1021/jacs.7b04695

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)Fe^V(NTs)]^? (1). The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe - N bond length of 1.65(4) ?, and an Fe - N vibration at 817 cm^-1. The reactivity of 1 was demonstrated in C - H bond functionalization and nitrene transfer reactions.

Full text of DOI:10.1021/jacs.7b04695

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Communication
A Mononuclear Nonheme Iron(V)-Imido Complex
Seungwoo Hong, Kyle D. Sutherlin, Anil Kumar Vardhaman, James J. Yan, Sora Park, Yong-Min Lee,
Soojeong Jang, Xiaoyan Lu, Takehiro Ohta, Takashi Ogura, Edward I. Solomon, and Wonwoo Nam
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 19 Jun 2017
Downloaded from http://pubs.acs.org on June 19, 2017
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AꢀMononuclearꢀNonhemeꢀIron(V)-ImidoꢀComplexꢀꢀ
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§
§
SeungwooꢀHong,† ꢀKyleꢀD.ꢀSutherlin, ꢀAnilꢀKumarꢀVardhaman, ꢀJamesꢀJ.ꢀYan, ꢀSoraꢀPark, ꢀYong-
,‡,#
,#
†
†
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, ,¶
†
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MinꢀLee, ꢀSoojeongꢀJang, ꢀXiaoyanꢀLu, ꢀTakehiroꢀOhta, ꢀTakashiꢀOgura, ꢀEdwardꢀI.ꢀSolomon,* ꢀandꢀ
,†
WonwooꢀNam* ꢀ
†ꢀ
DepartmentꢀofꢀChemistryꢀandꢀNanoꢀScience,ꢀEwhaꢀWomansꢀUniversity,ꢀSeoulꢀ03760,ꢀKoreaꢀ
‡ꢀ
§
DepartmentꢀofꢀChemistry,ꢀSookmyungꢀWomen’sꢀUniversity,ꢀSeoulꢀ04310,ꢀKoreaꢀ
DepartmentꢀofꢀChemistry,ꢀStanfordꢀUniversity,ꢀStanford,ꢀCaliforniaꢀ94305,ꢀUSAꢀ
‖
PicobiologyꢀInstitute,ꢀGraduateꢀSchoolꢀofꢀLifeꢀScience,ꢀUniversityꢀofꢀHyogo,ꢀRSC-UHꢀLPꢀCenter,ꢀHyogoꢀ679-5148,ꢀJa-
panꢀ
¶ꢀ
StanfordꢀSynchrotronꢀRadiationꢀLaboratory,ꢀStanfordꢀLinearꢀAcceleratorꢀCenter,ꢀCaliforniaꢀ94025,ꢀUSAꢀ
SupportingꢀInformationꢀPlaceholder
ꢀ
ABSTRACT:ꢀ Mononuclearꢀ nonhemeꢀ iron(V)-oxoꢀ com-
plexesꢀ haveꢀ beenꢀ reportedꢀ previously.ꢀ Herein,ꢀ weꢀ reportꢀ
theꢀfirstꢀexampleꢀofꢀaꢀmononuclearꢀnonhemeꢀiron(V)-imidoꢀ
complexꢀbearingꢀaꢀtetraamidoꢀmacrocyclicꢀligandꢀ(TAML),ꢀ
(TAML)Fe (NTs)] ꢀ(1).ꢀTheꢀspectroscopicꢀcharacterizationꢀ
ofꢀ 1ꢀ revealedꢀ anꢀ Sꢀ =ꢀ 1/2ꢀ Fe(V)ꢀ oxidationꢀ state,ꢀ anꢀ Fe-Nꢀ
bondꢀlengthꢀofꢀ1.65(4)ꢀÅ,ꢀandꢀanꢀFe-Nꢀvibrationꢀatꢀ817ꢀcm–1.ꢀ
Schemeꢀ 1.ꢀ Schematicꢀ Representationꢀ Showingꢀ theꢀ Syn-
thesis,ꢀ
[
Characterization,ꢀ
(TAML)Fe (NTs)] ꢀ
andꢀ
Reactivityꢀ
ofꢀ
V
–
V
–
[
Theꢀ reactivityꢀ ofꢀ 1ꢀ wasꢀ demonstratedꢀ inꢀ C–Hꢀ bondꢀ func-
tionalizationꢀandꢀnitreneꢀtransferꢀreactions.ꢀꢀ
n+
High-valentꢀiron-imidoꢀ(Fe =NR)ꢀspecies,ꢀwhichꢀareꢀiron-
oxoꢀ (Fe =O)ꢀ analogs, ꢀ haveꢀ beenꢀ proposedꢀ asꢀ reactiveꢀ
intermediatesꢀinꢀaziridinationꢀandꢀaminationꢀreactions. ꢀAꢀ
numberꢀofꢀsyntheticꢀiron-imidoꢀcomplexesꢀhaveꢀbeenꢀiso-
latedꢀandꢀcharacterizedꢀstructurallyꢀinꢀhemeꢀandꢀnonhemeꢀ
ironꢀsystems. ꢀRecently,ꢀaꢀmononuclearꢀnonhemeꢀiron(IV)-
imidoꢀ complexꢀ bearingꢀ aꢀ pentadentateꢀ N4Pyꢀ ligand,ꢀ
(N4Py)Fe (NTs)] ꢀ(N4Pyꢀ=ꢀ(N,N-bis(2-pyridylmethyl)-N-
ꢀ
n+
1
2,3
allowingꢀ usꢀ toꢀ characterizeꢀ itꢀ withꢀ variousꢀ spectroscopicꢀ
methods.ꢀTheꢀUV-visꢀspectrumꢀofꢀ1ꢀshowedꢀtwoꢀcharacter-
isticꢀabsorptionꢀbandsꢀatꢀλmaxꢀ=ꢀ595ꢀnmꢀ(εꢀ=ꢀ5200ꢀM ꢀcm )ꢀ
andꢀ 915ꢀ nmꢀ (εꢀ=ꢀ 2200ꢀ M ꢀ cm )ꢀ (Figureꢀ 1a).ꢀ Cold-sprayꢀ
ionizationꢀ time-of-flightꢀ massꢀ spectrumꢀ (CSI-MS)ꢀ ofꢀ 1ꢀ inꢀ
negativeꢀ modeꢀ exhibitedꢀ aꢀ prominentꢀ ionꢀ peakꢀ atꢀ m/zꢀ ofꢀ
595.1,ꢀwhoseꢀmassꢀandꢀisotopicꢀdistributionꢀpatternsꢀcor-
respondꢀ toꢀ [(TAML)Fe(NTs)] ꢀ (calculatedꢀ m/zꢀ ofꢀ 595.1)ꢀ
(Figureꢀ 1a,ꢀ inset;ꢀ Figureꢀ S1).ꢀ Aꢀ 15N-labelingꢀ experimentꢀ
–1
–1
4
–1
–1
IV
2+
[
bis(2-pyridyl)-methylamine;ꢀ NTsꢀ =ꢀ tosylimido),ꢀ whichꢀ isꢀ
IV
2+
5
–
anꢀ iron(IV)-oxoꢀ analogꢀ (i.e.,ꢀ [(N4Py)Fe (O)] ), ꢀ wasꢀ suc-
cessfullyꢀ synthesizedꢀ andꢀ investigatedꢀ inꢀ theꢀ C-Hꢀ bondꢀ
6
15
activationꢀandꢀnitreneꢀtransferꢀreactions. ꢀHowever,ꢀtoꢀtheꢀ
performedꢀ withꢀ PhI NTsꢀ resultedꢀ inꢀ oneꢀ massꢀ unitꢀ shiftꢀ
fromꢀm/zꢀ595.1ꢀtoꢀ596.1ꢀ(Figureꢀ1a,ꢀinset),ꢀindicatingꢀthatꢀ
1ꢀ containsꢀ anꢀ NTsꢀ group.ꢀ X-bandꢀ EPRꢀ spectraꢀ ofꢀ 1ꢀ dis-
bestꢀ ofꢀ ourꢀ knowledge,ꢀ high-valentꢀ iron(V)-imidoꢀ com-
plexesꢀ haveꢀ notꢀ beenꢀ reportedꢀ inꢀ nonhemeꢀ ironꢀ models.ꢀ
Encouragedꢀ byꢀ theꢀ previousꢀ reportꢀ ofꢀ theꢀ iron(V)-oxoꢀ
complexꢀbearingꢀaꢀtetraamidoꢀmacrocyclicꢀligandꢀ(TAML),ꢀ
(TAML)Fe (O)] , ꢀweꢀattemptedꢀtoꢀsynthesizeꢀanꢀiron(V)-
imidoꢀcomplexꢀusingꢀtheꢀTAMLꢀsupportingꢀligand.ꢀHerein,ꢀ
weꢀ reportꢀ theꢀ firstꢀ exampleꢀ ofꢀ aꢀ mononuclearꢀ nonhemeꢀ
playedꢀanꢀisotropicꢀsignalꢀatꢀgꢀ=ꢀ2.00ꢀinꢀCH CNꢀandꢀtheꢀani-
3
sotropicꢀsignalsꢀwithꢀgxx,ꢀ=ꢀ2.04,ꢀgyyꢀ=ꢀ2.00,ꢀandꢀgzzꢀ=1.96ꢀinꢀ
butyronitrileꢀ (Figureꢀ S2),ꢀ indicatingꢀ aꢀ low-spinꢀ (Sꢀ =ꢀ 1/2)ꢀ
stateꢀofꢀanꢀiron(V)ꢀion,ꢀasꢀreportedꢀinꢀtheꢀiron(V)-oxoꢀana-
V
– 7
[
V
– 7
log,ꢀ[(TAML)Fe (O)] . ꢀ
V
–
iron(V)-imidoꢀ complex,ꢀ [(TAML)Fe (NTs)] ꢀ (1)ꢀ (Schemeꢀ
Theꢀ resonanceꢀ Ramanꢀ (rR)ꢀ spectrumꢀ ofꢀ 1,ꢀ uponꢀ 442ꢀ
nm-excitationꢀinꢀCH CNꢀatꢀ–40ꢀ°C,ꢀexhibitedꢀanꢀisotopicallyꢀ
sensitiveꢀdoubletꢀfeatureꢀcenteredꢀatꢀ817ꢀcm ꢀ(FigureꢀS3),ꢀ
whichꢀshiftedꢀtoꢀaꢀnewꢀdoubletꢀcenteredꢀatꢀ796ꢀcm ꢀuponꢀ
N-labelingꢀofꢀ1ꢀ(FigureꢀS3;ꢀseeꢀtheꢀdetailedꢀdiscussionꢀinꢀ
Supplementaryꢀ Resultsꢀ andꢀ Analysisꢀ inꢀ SI).ꢀ Thisꢀ isotopicꢀ
shiftꢀofꢀ21ꢀcm ꢀisꢀinꢀaꢀgoodꢀagreementꢀwithꢀtheꢀcalculatedꢀ
1).ꢀꢀ
3
–
1
AdditionꢀofꢀsolidꢀN-tosyliminophenyliodinaneꢀ(PhINTs;ꢀ
III
o
–1
3
ꢀequiv)ꢀtoꢀtheꢀCH
3
CNꢀsolutionꢀofꢀNa[(TAML)Fe ]ꢀatꢀ15ꢀ Cꢀ
15
affordedꢀanꢀimmediateꢀcolorꢀchangeꢀfromꢀorangeꢀtoꢀdarkꢀ
greenꢀ(seeꢀExperimentalꢀSectionꢀinꢀSupportingꢀInformationꢀ
SI)ꢀforꢀdetailedꢀsyntheticꢀprocedures).ꢀTheꢀintermediate,ꢀ
–1
(
o
–1
denotedꢀasꢀ1,ꢀwasꢀrelativelyꢀstableꢀatꢀ25ꢀ Cꢀ(t1/2ꢀ~12ꢀmin),ꢀ
valueꢀofꢀ22ꢀcm ꢀforꢀaꢀdiatomicꢀFe-Nꢀoscillatorꢀestimatedꢀbyꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
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ꢀ
ꢀ
Figureꢀ 2.ꢀ (a)ꢀ XASꢀ dataꢀ ofꢀ 1ꢀ (pre-edgeꢀ =ꢀ 51ꢀ units)ꢀ (blueꢀ line),ꢀ
Fe (TAML)] ꢀ (blackꢀ line),ꢀ andꢀ 70%ꢀ [(TAML)Fe (O)] ꢀ (48ꢀ units,ꢀ
III
–
Figureꢀ 1.ꢀ (a)ꢀ UV-visꢀ spectraꢀ ofꢀ [Fe (TAML)] ꢀ (0.25ꢀ mM;ꢀ blackꢀ
line)ꢀandꢀ1ꢀ(blueꢀline)ꢀproducedꢀbyꢀreactingꢀ[Fe (TAML)] ꢀ(0.25ꢀ
mM)ꢀwithꢀsolidꢀPhINTsꢀ(3ꢀequiv)ꢀinꢀCH CNꢀatꢀ15ꢀ°C.ꢀInsetsꢀshowꢀ
CSI-MSꢀspectraꢀwithꢀtheꢀisotopicꢀdistributionꢀpatternsꢀofꢀtheꢀpeaksꢀ
atꢀm/zꢀofꢀ595.1ꢀforꢀ1- NTsꢀ(leftꢀpanel)ꢀandꢀm/zꢀofꢀ596.1ꢀforꢀ1-
15NTsꢀ (rightꢀ panel).ꢀ (b)ꢀ Mössbauerꢀ spectrumꢀ (blackꢀ dottedꢀ line)ꢀ
forꢀ1ꢀrecordedꢀatꢀ6ꢀKꢀandꢀ0ꢀT.ꢀTheꢀblackꢀsolidꢀlineꢀisꢀaꢀsuperposi-
tionꢀofꢀtheꢀsimulatedꢀ1ꢀ(85ꢀ%,ꢀblueꢀline)ꢀandꢀtheꢀdecayꢀproductꢀofꢀ
III
–
V
–
[
III
–
fitꢀofꢀthisꢀpre-edgeꢀisꢀgivenꢀinꢀFigureꢀS7)ꢀ(greenꢀline).ꢀInsetꢀshowsꢀ
theꢀexpansionꢀofꢀpre-edgeꢀregion.ꢀ(b)ꢀFourierꢀtransformꢀandꢀDFTꢀ
structureꢀ(inset)ꢀofꢀ1ꢀ(blackꢀline)ꢀwithꢀfitsꢀ(blueꢀline).ꢀRawꢀEXAFSꢀ
dataꢀ areꢀ inꢀ Figureꢀ S10.ꢀ Theꢀ EXAFSꢀ dataꢀ wereꢀ fitꢀ withꢀ 30%ꢀ FeIVꢀ
decay,ꢀconsistentꢀwithꢀparallelꢀMössbauerꢀdata.ꢀInsetꢀshowsꢀtheꢀ
DFT-optimizedꢀstructureꢀofꢀ1.ꢀ
3
14
1
ꢀ(15%,ꢀredꢀline)ꢀ(seeꢀFiguresꢀS4ꢀandꢀS5).ꢀ
ferentꢀamountsꢀofꢀ1ꢀandꢀitsꢀdecayꢀproductꢀ(Figuresꢀ2,ꢀS6ꢀ–ꢀ
S10ꢀandꢀTableꢀS2).ꢀTheꢀnormalizedꢀX-rayꢀabsorptionꢀnear-
edgeꢀstructureꢀ(XANES)ꢀatꢀtheꢀFeꢀK-edgeꢀofꢀ1ꢀdisplayedꢀanꢀ
edgeꢀatꢀaꢀhigherꢀenergyꢀthanꢀtheꢀ[Fe (TAML)] ꢀreferenceꢀ
edgeꢀandꢀcomparableꢀtoꢀtheꢀ[(TAML)Fe (O)] ꢀedgeꢀ(Figureꢀ
-
1ꢀ
Hooke’sꢀLawꢀandꢀtheꢀDFT-calculatedꢀvalueꢀofꢀ20ꢀcm (Ta-
bleꢀ S1).ꢀ Theꢀ rRꢀ dataꢀ indicateꢀ thatꢀ theꢀ ironꢀ andꢀ nitrogenꢀ
bondꢀinꢀ1 possessesꢀdoubleꢀbondꢀcharacterꢀ(videꢀinfra),ꢀasꢀ
shownꢀ inꢀ mononuclearꢀ nonhemeꢀ iron(IV)-oxoꢀ complexesꢀ
withꢀν(Fe=O)ꢀvibrationsꢀinꢀtheꢀrageꢀofꢀ~810ꢀ–ꢀ840ꢀcm . ꢀItꢀ
isꢀworthꢀnotingꢀthatꢀiron-imidoꢀcomplexesꢀwithꢀaꢀpseudo-
III
–
V
–
7
a
2
a), ꢀindicatingꢀaꢀformalꢀ+5ꢀoxidationꢀstateꢀofꢀtheꢀironꢀionꢀ
asꢀdeterminedꢀfromꢀMössbauer.ꢀTheꢀpre-edgeꢀenergyꢀofꢀ1ꢀ
7113.2ꢀeV)ꢀisꢀalsoꢀhigherꢀthanꢀtheꢀpre-edgeꢀenergyꢀofꢀtheꢀ
–
1 8
(
[
tetrahedralꢀgeometryꢀandꢀC ꢀsymmetryꢀshowꢀFe-Nꢀstretch-
s
III
–
IV
Fe (TAML)] ꢀ referenceꢀ (7112.1ꢀ eV)ꢀ andꢀ theꢀ Fe ꢀ decayꢀ
productꢀ(7112.9ꢀeV)ꢀandꢀsimilarꢀtoꢀtheꢀpre-edgeꢀenergyꢀofꢀ
–
1
ingꢀ vibrationsꢀ atꢀ >1000ꢀ cm ꢀ withꢀ shortꢀ Fe-Nꢀ bondꢀ dis-
tancesꢀ (~1.63ꢀ Å)ꢀ andꢀ nearlyꢀ linearꢀ Fe-N-Rꢀ anglesꢀ (videꢀ
infra),ꢀthoughꢀitꢀshouldꢀbeꢀnotedꢀthatꢀtheseꢀgeometricꢀpa-
rametersꢀ areꢀ dependentꢀ onꢀ theꢀ electronicꢀ structureꢀ andꢀ
spinꢀstateꢀofꢀtheꢀcomplexesꢀinꢀadditionꢀtoꢀtheirꢀcoordina-
tionꢀnumber.4,9,10ꢀꢀ
V
–
7a
V
[
(
(TAML)Fe (O)] ꢀ (7113.3ꢀ eV), ꢀ consistentꢀ withꢀ anꢀ Fe ꢀ
Figureꢀ2a,ꢀinset).ꢀFitsꢀtoꢀtheꢀpre-edgeꢀfeatureꢀatꢀ7113.2ꢀeVꢀ
ofꢀ1ꢀfoundꢀaꢀtotalꢀpre-edgeꢀintensityꢀofꢀ51ꢀunits,ꢀwhichꢀisꢀ
normalizedꢀ toꢀ 52ꢀ unitsꢀ toꢀ accountꢀ forꢀ theꢀ 15-30%ꢀ decayꢀ
productꢀ inꢀ theꢀ sample,ꢀ similarꢀ toꢀ [(TAML)Fe (O)] ꢀ (48ꢀ
units,ꢀnormalizedꢀtoꢀ60ꢀunitsꢀafterꢀaccountingꢀforꢀ30%ꢀde-
cay;ꢀ seeꢀ Figureꢀ S7). ꢀ Theꢀ normalizationꢀ procedureꢀ isꢀ ex-
plainedꢀ inꢀ theꢀ SI.ꢀ Theꢀ lowerꢀ pre-edgeꢀ intensityꢀ forꢀ 1ꢀ vsꢀ
(TAML)Fe (O)] ꢀ reflectsꢀ itsꢀ weakerꢀ axialꢀ bondingꢀ (videꢀ
infra).ꢀ
Directꢀevidenceꢀforꢀtheꢀiron-tosylimidoꢀunitꢀisꢀfoundꢀinꢀ
V
–
57
Mössbauerꢀdataꢀwereꢀcollectedꢀonꢀthreeꢀ Feꢀsamplesꢀofꢀ
ꢀ atꢀ 6ꢀ K,ꢀ asꢀ shownꢀ inꢀ Figuresꢀ 1bꢀ andꢀ S4.ꢀ Althoughꢀ thereꢀ
wasꢀaꢀdegreeꢀofꢀvariabilityꢀtoꢀtheseꢀsamplesꢀdueꢀtoꢀinstabil-
ity,ꢀtheꢀthreeꢀdataꢀsetsꢀcouldꢀbeꢀsimultaneouslyꢀfitꢀtoꢀvari-
ableꢀamountsꢀofꢀtheꢀsameꢀtwoꢀspeciesꢀwithꢀparametersꢀδꢀ=ꢀ
1
7a
V
–
[
–
0.40ꢀmm/sꢀandꢀΔE
Q
ꢀ=ꢀ3.83ꢀmm/sꢀandꢀδꢀ=ꢀ–0.09ꢀmm/sꢀandꢀ
ΔE ꢀ =ꢀ 3.23ꢀ mm/s,ꢀ respectively;ꢀ thoseꢀ areꢀ consistentꢀ withꢀ
Q
theꢀ analysisꢀ ofꢀ theꢀ extendedꢀ X-rayꢀ absorptionꢀ fineꢀ struc-
tureꢀ(EXAFS)ꢀregionꢀ(Figuresꢀ2bꢀandꢀS10).ꢀVaryingꢀtheꢀfirstꢀ
shellꢀ atꢀ 0.70ꢀ –ꢀ 0.85ꢀ Nꢀ scattererꢀ (determinedꢀ fromꢀ Möss-
bauer),ꢀ theꢀ fitsꢀ acrossꢀ allꢀ dataꢀ setsꢀ giveꢀ anꢀ Fe-Nꢀ bondꢀ
lengthꢀofꢀ1.65ꢀ±ꢀ0.04ꢀÅꢀ(TableꢀS3).ꢀThisꢀisꢀlongerꢀthanꢀtheꢀ
theꢀXASꢀdataꢀonꢀparallelꢀsamplesꢀ(videꢀinfra).ꢀTheꢀparame-
tersꢀforꢀtheꢀlatterꢀcomponent,ꢀwhichꢀcomprisedꢀ15ꢀ–ꢀ30%ꢀ
ofꢀ theꢀ Mössbauerꢀ spectrum,ꢀ areꢀ identicalꢀ toꢀ thoseꢀ meas-
uredꢀforꢀtheꢀdecayꢀproductꢀofꢀ1ꢀ(FigureꢀS5).ꢀTheꢀparame-
tersꢀforꢀtheꢀformerꢀcomponent,ꢀaccountingꢀforꢀ70ꢀ–ꢀ85%ꢀofꢀ
theꢀspectrum,ꢀareꢀveryꢀsimilarꢀtoꢀthoseꢀpreviouslyꢀreportedꢀ
V
– 7a
Fe-Oꢀ bondꢀ lengthꢀ ofꢀ 1.58ꢀ Åꢀ foundꢀ forꢀ [(TAML)Fe (O)] , ꢀ
whichꢀleadsꢀtoꢀlessꢀFeꢀ4pꢀmixingꢀinꢀtheꢀunoccupiedꢀorbitalsꢀ
ofꢀ 1ꢀ andꢀ decreasedꢀ pre-edgeꢀ intensity.ꢀ Twoꢀ otherꢀ shellsꢀ
showedꢀfourꢀN/Oꢀscatterersꢀatꢀ1.87ꢀÅꢀandꢀeightꢀCꢀscatter-
ersꢀatꢀ2.84ꢀÅ,ꢀconsistentꢀwithꢀlowꢀZꢀatomsꢀfromꢀtheꢀTAMLꢀ
V
–
forꢀ[(TAML)Fe (O)] ꢀ(e.g.,ꢀδꢀ=ꢀ–0.42ꢀmm/sꢀandꢀΔEQꢀ=ꢀ4.25ꢀ
mm/s), ꢀleadingꢀusꢀtoꢀassignꢀtheꢀformalꢀoxidationꢀstateꢀofꢀ
7a
+5ꢀforꢀtheꢀironꢀionꢀinꢀ1.ꢀ
X-rayꢀ absorptionꢀ spectroscopyꢀ (XAS)ꢀ dataꢀ wereꢀ alsoꢀ
collectedꢀonꢀtheseꢀthreeꢀdifferentꢀ Feꢀsamplesꢀhavingꢀdif-
V
–
ligandꢀ(TableꢀS3)ꢀandꢀsimilarꢀtoꢀtheꢀfitꢀforꢀ[(TAML)Fe (O)] .ꢀ
TheꢀfitꢀalsoꢀfoundꢀanꢀSꢀscattererꢀatꢀ2.95ꢀÅ,ꢀconsistentꢀwithꢀ
57
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Journal of the American Chemical Society
Schemeꢀ 2.ꢀ Reactionsꢀ ofꢀ 1ꢀ inꢀ theꢀ Aminationꢀ andꢀ Nitreneꢀ
TransferꢀReactionsꢀꢀ
1
2
3
4
5
6
7
8
9
H
H
V
–
S
[(TAML)Fe (NTs)]
1)
Ph
Me
(
i
ii
H
NHTs
[
(TAML)FeIII]–
NTs
S
Ph
Me
ꢀ
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
IV
NTsꢀ inꢀ theꢀ bentꢀ structure,ꢀ leadingꢀ theꢀ Fe ꢀ complexꢀ toꢀ
adoptꢀ aꢀ moreꢀ linearꢀ structureꢀ thatꢀ hasꢀ πꢀ ratherꢀ thanꢀ σꢀ
overlapꢀ betweenꢀ theꢀ Feꢀ andꢀ NTsꢀ (Figureꢀ S18).ꢀ Thus,ꢀ theꢀ
lackꢀofꢀaꢀtransꢀaxialꢀligandꢀinꢀ1ꢀallowsꢀaꢀmoreꢀbentꢀFe-N-Sꢀ
unitꢀthatꢀreplacesꢀanꢀFe-Nꢀπꢀbondꢀwithꢀaꢀstrongerꢀσꢀbondꢀ
ꢀ
Figureꢀ3.ꢀ(a)ꢀPlotꢀofꢀlog(k
reactionsꢀofꢀ1ꢀ(TableꢀS5).ꢀ(b)ꢀHammettꢀplotꢀofꢀlog(krel)ꢀagainstꢀσ
2
’)ꢀagainstꢀC–HꢀBDEꢀofꢀsubstratesꢀforꢀtheꢀ
p
ꢀ
ofꢀpara-substitutedꢀthioanisoleꢀderivativesꢀinꢀtheꢀnitreneꢀtransferꢀ
reactionꢀofꢀ1ꢀwithꢀthioanisoleꢀderivativesꢀinꢀCH CNꢀatꢀ15ꢀ°Cꢀ(Tableꢀ
3
IV
S6).ꢀ
relativeꢀtoꢀtheꢀFe ꢀcomplexꢀ(seeꢀtheꢀSIꢀforꢀmoreꢀdetails).ꢀ
NoteꢀthatꢀthisꢀbendingꢀisꢀnotꢀaꢀJahn-Tellerꢀ(J-T)ꢀdistortion:ꢀ
inꢀtheꢀ~C4vꢀsymmetryꢀofꢀ1ꢀwithꢀtheꢀFe-N-Sꢀangleꢀconstrai-
nedꢀatꢀnearꢀlinearꢀ(13ꢀkcal/molꢀhigherꢀinꢀenergyꢀthanꢀtheꢀ
freelyꢀoptimizedꢀstructure),ꢀtheꢀgroundꢀstateꢀisꢀ EꢀandꢀaꢀJ-Tꢀ
distortingꢀ modeꢀ wouldꢀ haveꢀ toꢀ haveꢀ aꢀ symmetryꢀ thatꢀ isꢀ
containedꢀinꢀtheꢀsymmetricꢀdirectꢀproductꢀofꢀEꢀxꢀEꢀ(=ꢀA
ꢀ+ꢀB ).ꢀTheꢀnormalꢀmodeꢀassociatedꢀwithꢀbendingꢀofꢀtheꢀ
Fe-N-SꢀunitꢀhasꢀEꢀsymmetryꢀandꢀisꢀnotꢀJ-Tꢀactive.ꢀ
theꢀtosylimidoꢀgroupꢀbindingꢀtoꢀtheꢀiron.ꢀFullꢀfitꢀparame-
tersꢀforꢀtheꢀdifferentꢀsamplesꢀareꢀgivenꢀinꢀTableꢀS4.ꢀꢀ
Densityꢀfunctionalꢀtheoryꢀ(DFT)ꢀcalculationsꢀwereꢀusedꢀ
toꢀcorrelateꢀtoꢀtheꢀaboveꢀdataꢀandꢀfurtherꢀdefineꢀtheꢀelec-
tronicꢀstructureꢀofꢀ1.ꢀ1ꢀandꢀ[(TAML)Fe (O)] forꢀcalibrationꢀ
purposesꢀ wereꢀ geometricallyꢀ optimizedꢀ onꢀ theꢀ Sꢀ =ꢀ 1/2ꢀ
surfaceꢀusingꢀtheꢀBP86ꢀandꢀB3LYPꢀfunctionalsꢀinꢀcombina-
tionꢀ withꢀ theꢀ 6-311G+(3df)ꢀ basisꢀ setꢀ onꢀ Feꢀ andꢀ theꢀ tosy-
2
V
–ꢀ
1
ꢀ+ꢀ
B
1
2
11
Theꢀreactivityꢀofꢀ1ꢀwasꢀinvestigatedꢀinꢀC–Hꢀbondꢀactiva-
tionꢀandꢀnitreneꢀtransferꢀreactions.ꢀAdditionꢀofꢀxantheneꢀtoꢀ
aꢀCH CNꢀsolutionꢀofꢀ1ꢀresultedꢀinꢀtheꢀdisappearanceꢀofꢀtheꢀ
limidoꢀ Nꢀ andꢀ theꢀ 6-311Gꢀ basisꢀ setꢀ onꢀ allꢀ otherꢀ atoms. ꢀ
FurtherꢀcomputationalꢀdetailsꢀcanꢀbeꢀfoundꢀinꢀtheꢀSI.ꢀTableꢀ
S1ꢀ summarizesꢀ theꢀ resultsꢀ ofꢀ theseꢀ calculationsꢀ andꢀ theꢀ
comparisonꢀwithꢀtheꢀrelevantꢀexperimentalꢀdata.ꢀTheꢀBP86ꢀ
calculationꢀgivesꢀtheꢀbestꢀagreementꢀwithꢀexperiment.ꢀTheꢀ
electronicꢀstructureꢀ(FigureꢀS13)ꢀassociatedꢀwithꢀthisꢀcal-
culationꢀ isꢀ aꢀ [(TAML)Fe (NTs)] ꢀ (seeꢀ theꢀ Supplementaryꢀ
Resultsꢀ andꢀ Analysisꢀ inꢀ theꢀ SIꢀ forꢀ aꢀ fullꢀ discussionꢀ ofꢀ theꢀ
electronicꢀstructureꢀofꢀ1ꢀandꢀaꢀdescriptionꢀofꢀitsꢀFe-Nꢀbond-
ing).ꢀBasedꢀonꢀtheꢀspectroscopicꢀcharacterizationꢀandꢀDFTꢀ
calculations,ꢀ weꢀ concludeꢀ thatꢀ anꢀ iron(V)-imidoꢀ complex,ꢀ
3
absorptionꢀbandsꢀatꢀ595ꢀandꢀ915ꢀnmꢀdueꢀtoꢀ1ꢀ(FigureꢀS19).ꢀ
Theꢀfirst-orderꢀrateꢀconstantsꢀincreasedꢀlinearlyꢀwithꢀtheꢀ
increaseꢀofꢀxantheneꢀconcentrationꢀ(FigureꢀS20),ꢀgivingꢀaꢀ
–
1
–1
V
–
second-orderꢀrateꢀconstantꢀ(k
kineticꢀisotopeꢀeffectꢀ(KIE)ꢀvalueꢀofꢀ11(1)ꢀwasꢀdeterminedꢀ
inꢀtheꢀoxidationꢀofꢀxantheneꢀandꢀxanthene-d ꢀbyꢀ1ꢀ(Figureꢀ
S21);ꢀaꢀKIEꢀvalueꢀofꢀ11(1)ꢀwasꢀobtainedꢀinꢀtheꢀoxidationꢀofꢀ
ethylbenzeneꢀ byꢀ theꢀ iron(V)-oxoꢀ analog,ꢀ
2
)ꢀofꢀ4.7(4)ꢀM ꢀs ꢀatꢀ15ꢀ°C.ꢀAꢀ
2
V
7d
V
–
[(TAML)Fe (O)]¯. ꢀWeꢀalsoꢀdeterminedꢀsecond-orderꢀrateꢀ
constantsꢀ inꢀ theꢀ oxidationꢀ ofꢀ otherꢀ substrates,ꢀ suchꢀ asꢀ
,10-dihydroanthraceneꢀ(DHA),ꢀindene,ꢀandꢀfluoreneꢀ(Fig-
[
(TAML)Fe (NTs)] ꢀ(1),ꢀwasꢀsuccessfullyꢀsynthesizedꢀinꢀtheꢀ
reactionꢀ ofꢀ [Fe (TAML)] ꢀ andꢀ PhINTsꢀ (Schemeꢀ 1).ꢀ Noteꢀ
thatꢀanꢀequivalentꢀDFTꢀcalculationꢀusingꢀtheꢀB3LYPꢀfunc-
III
–
9
IV
ureꢀS20ꢀandꢀTableꢀS5).ꢀAsꢀshoꢀwnꢀinꢀFigureꢀ3a,ꢀaꢀgoodꢀlin-
earꢀ correlationꢀ betweenꢀ theꢀ reactionꢀ ratesꢀ andꢀ theꢀ C–Hꢀ
bondꢀ dissociationꢀ energiesꢀ (BDEs)ꢀ ofꢀ substratesꢀ wasꢀ ob-
tained.ꢀ Basedꢀ onꢀ theꢀ observationsꢀ ofꢀ theꢀ largeꢀ KIEꢀ valueꢀ
andꢀ theꢀ goodꢀ correlationꢀ betweenꢀ theꢀ reactionꢀ ratesꢀ andꢀ
theꢀC–HꢀBDEsꢀofꢀsubstrates,ꢀweꢀproposeꢀthatꢀaꢀhydrogenꢀ
atomꢀ (H-atom)ꢀ abstractionꢀ fromꢀ theꢀ C-Hꢀ bondsꢀ ofꢀ sub-
stratesꢀbyꢀ1ꢀisꢀtheꢀrate-determiningꢀstepꢀ(r.d.s.)ꢀinꢀtheꢀC-Hꢀ
bondꢀactivationꢀreactions,ꢀasꢀalsoꢀobservedꢀinꢀtheꢀC-Hꢀbondꢀ
activationꢀ ofꢀ hydrocarbonsꢀ byꢀ itsꢀ iron(V)-oxoꢀ analog,ꢀ
[(TAML)Fe (O)]¯. ꢀProductꢀanalysisꢀofꢀtheꢀfluoreneꢀoxida-
tionꢀ byꢀ 1ꢀ revealedꢀ thatꢀ theꢀ oxidizedꢀ productꢀ ofꢀ fluoreneꢀ
wasꢀfluorene-N(H)Tsꢀasꢀaꢀmajorꢀproductꢀ(~90%ꢀyield)ꢀandꢀ
theꢀ reducedꢀ productꢀ ofꢀ 1ꢀ wasꢀ theꢀ startingꢀ [Fe (TAML)] ꢀ
complexꢀ(FigureꢀS22).ꢀWeꢀthereforeꢀconcludeꢀthatꢀtheꢀami-
nationꢀ reactionꢀ byꢀ 1ꢀ occursꢀ viaꢀ aꢀ H-atomꢀ abstractionꢀ ofꢀ
substratesꢀ toꢀ giveꢀ theꢀ aminatedꢀ productꢀ andꢀ theꢀ startingꢀ
tionalꢀ gaveꢀ anꢀ Fe -tosylimidoꢀ radicalꢀ withꢀ spectralꢀ fea-
turesꢀthatꢀdoꢀnotꢀagreeꢀwithꢀexperimentꢀ(seeꢀSI).ꢀ
Theꢀ electronicꢀ structuresꢀ calculatedꢀ forꢀ 1ꢀ andꢀ itsꢀ oxoꢀ
7a
analog ꢀusingꢀBP86ꢀgiveꢀinsightꢀintoꢀtheꢀnatureꢀofꢀtheꢀFe-Nꢀ
bond.ꢀ Theꢀ Fe-Nꢀ bondꢀ ofꢀ 1ꢀ isꢀ longerꢀ thanꢀ thatꢀ ofꢀ theꢀ oxoꢀ
analogueꢀ (1.65ꢀ Åꢀ vsꢀ 1.58ꢀ Å),ꢀ consistentꢀ withꢀ itsꢀ lowerꢀ
Mayerꢀbondꢀorderꢀ(1.686ꢀvsꢀ1.950),ꢀdueꢀtoꢀoneꢀN(Ts)ꢀor-
bitalꢀbeingꢀunavailableꢀforꢀbondingꢀwithꢀFeꢀasꢀitꢀisꢀdomi-
nantlyꢀinvolvedꢀinꢀtheꢀN-Tsꢀbondꢀ(seeꢀSI).ꢀAꢀpreviousꢀstudyꢀ
describedꢀdifferencesꢀinꢀbondingꢀbetweenꢀtheꢀSꢀ=ꢀ1ꢀcom-
V
7d
IV
2+
IV
2+
plexesꢀ [(N4Py)Fe (O)] ꢀ andꢀ [(N4Py)Fe (NTs)] ,ꢀ alsoꢀ
6
a
attributedꢀtoꢀtheꢀTsꢀgroup. ꢀInterestingly,ꢀinꢀthatꢀcase,ꢀgo-
IV
IV
ingꢀfromꢀtheꢀFe =OꢀtoꢀtheꢀFe -NTsꢀwasꢀfoundꢀtoꢀincreaseꢀ
theꢀbondꢀlengthꢀbyꢀaꢀlargerꢀamount,ꢀfromꢀ1.64ꢀtoꢀ1.73ꢀÅ,ꢀ
andꢀtheꢀFe-Nꢀbondꢀwasꢀdescribedꢀasꢀconsistingꢀprimarilyꢀofꢀ
πꢀbondingꢀwithꢀonlyꢀaꢀweakꢀσꢀbond. ꢀInꢀaddition,ꢀMayerꢀ
bondꢀ ordersꢀ calculatedꢀ forꢀ theꢀ Fe ꢀ structuresꢀ reported ꢀ
decreaseꢀ moreꢀ inꢀ goingꢀ fromꢀ oxoꢀ toꢀ NTs,ꢀ fromꢀ 1.931ꢀ toꢀ
1.528.ꢀTheꢀsix-coordinateꢀ[(N4Py)Fe (NTs)] ꢀcomplexꢀhasꢀ
aꢀmoreꢀlinearꢀcalculatedꢀFe-N-Sꢀangleꢀ(152°)ꢀrelativeꢀtoꢀ1ꢀ
(126°),ꢀdueꢀtoꢀitsꢀadditionalꢀligandꢀtransꢀtoꢀtheꢀNTsꢀ(seeꢀtheꢀ
III
–
6a
IV
6a
III
–
[
Fe (TAML)] ꢀcomplexꢀ(seeꢀSchemeꢀ2,ꢀreactionꢀi).ꢀ
IV
2+
1ꢀwasꢀalsoꢀshownꢀtoꢀtransferꢀitsꢀNTsꢀgroupꢀtoꢀthioani-
soleꢀandꢀpara-X-substitutedꢀthioanisolesꢀ(Xꢀ=ꢀOMe,ꢀMe,ꢀandꢀ
Cl).ꢀTheꢀkobsꢀofꢀtheꢀsulfimidationꢀreactionꢀwasꢀdeterminedꢀ
byꢀpseudo-first-orderꢀfittingꢀofꢀtheꢀdecayꢀofꢀ1ꢀmonitoredꢀatꢀ
SIꢀ forꢀ details).ꢀ Thisꢀ transꢀ ligandꢀ interactsꢀ withꢀ theꢀ Feꢀ dz2
ꢀ
5
95ꢀ andꢀ 915ꢀ nmꢀ (Figureꢀ S23a).ꢀ Theꢀ kobsꢀ valueꢀ increasedꢀ
orbital,ꢀmakingꢀitꢀlessꢀavailableꢀforꢀσꢀtypeꢀbondingꢀwithꢀtheꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
linearlyꢀwithꢀincreasingꢀthioanisoleꢀconcentration,ꢀafford- SLACꢀNationalꢀAcceleratorꢀLaboratory,ꢀisꢀsupportedꢀbyꢀtheꢀ
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
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
–2
–1 –1
o
ingꢀaꢀk
andꢀTableꢀS6).ꢀTheꢀproductꢀanalysisꢀofꢀtheꢀthioanisoleꢀoxi-
dationꢀ byꢀ 1ꢀ revealedꢀ theꢀ formationꢀ ofꢀ PhS(=NTs)CH
2
ꢀvalueꢀofꢀ2.6(2)ꢀ×ꢀ10 ꢀM ꢀs ꢀatꢀ15ꢀ Cꢀ(FigureꢀS23bꢀ
U.S.ꢀDOEꢀunderꢀContractꢀNo.ꢀDE-AC02-76SF00515.ꢀꢀ
REFERENCESꢀ
3
ꢀ
(~85%ꢀ yield).ꢀ Inꢀ addition,ꢀ onꢀ theꢀ basisꢀ ofꢀ spectroscopicꢀ
characterizationꢀofꢀtheꢀdecayꢀproductꢀofꢀ1ꢀusingꢀUV-vis,ꢀX-
bandꢀ EPR,ꢀ andꢀ ESI-MSꢀ (Figuresꢀ S23aꢀ andꢀ S24),ꢀ weꢀ con-
cludeꢀthatꢀ1ꢀtransfersꢀitsꢀNTsꢀgroupꢀtoꢀthioanisoleꢀtoꢀgiveꢀ
1
.
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4. (a)ꢀThomas,ꢀC.ꢀM.;ꢀMankad,ꢀN.ꢀP.;ꢀPeters,ꢀJ.ꢀC.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ
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III
–
theꢀPhS(=NTs)CH ꢀandꢀ[Fe (TAML)] ꢀproductsꢀ(Schemeꢀ2,ꢀ
3
632.ꢀꢀ
.
reactionꢀ ii).ꢀ Theꢀ electrophilicꢀ characterꢀ ofꢀ theꢀ iron(V)-
imidoꢀcomplexꢀwasꢀalsoꢀdemonstratedꢀbyꢀtheꢀρꢀvalueꢀofꢀ–
(a)ꢀ Saouma,ꢀ C.ꢀ T.;ꢀ Peters,ꢀ J.ꢀ C.ꢀ Coord.ꢀ Chem.ꢀ Rev.ꢀ 2011,ꢀ 255,ꢀ
0
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6
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0
20.ꢀ(b)ꢀChe,ꢀC.-M.;ꢀLo,ꢀV.ꢀK.-Y.;ꢀZhou,ꢀC.-Y.;ꢀHuang,ꢀJ.-S.ꢀChem.ꢀSoc.ꢀ
1
.8ꢀ inꢀ theꢀ sulfimidationꢀ reactionꢀ ofꢀ para-X-substitutedꢀ
thioanisolesꢀbyꢀ1ꢀ(Figureꢀ3b).ꢀInꢀtheꢀreactivityꢀstudies,ꢀweꢀ
haveꢀshownꢀthatꢀtheꢀiron(V)-imidoꢀcomplexꢀisꢀcapableꢀofꢀC-
Hꢀbondꢀactivationꢀandꢀnitreneꢀtransferꢀreactions.ꢀ
. (a)ꢀEikey,ꢀR.ꢀA.;ꢀAbu-Omar,ꢀM.ꢀM.ꢀCoord.ꢀChem.ꢀRev.ꢀ2003,ꢀ243,ꢀ
Inꢀ summary,ꢀ weꢀ haveꢀ reportedꢀ theꢀ firstꢀ syntheticꢀ
mononuclearꢀ nonhemeꢀ iron(V)-imidoꢀ complexꢀ thatꢀ isꢀ ca-
pableꢀ ofꢀ C–Hꢀ functionalizationꢀ ofꢀ hydrocarbonsꢀ andꢀ theꢀ
sulfimidationꢀ ofꢀ sulfur-containingꢀ substrates.ꢀ 1ꢀ isꢀ moreꢀ
IV
2+
reactiveꢀ thanꢀ [(N Py)Fe (NTs)] ꢀ inꢀ C-Hꢀ functionaliza-
4
6c
tion, ꢀwhichꢀisꢀexpectedꢀforꢀsuchꢀanꢀelectrophilicꢀreactionꢀ
givenꢀ theꢀ higherꢀ effectiveꢀ chargeꢀ onꢀ theꢀ Fe.ꢀHowever,ꢀ in-
terestingly,ꢀ 1ꢀ isꢀ lessꢀ reactiveꢀ thanꢀ [(N Py)Fe (NTs)] ꢀ inꢀ
sulfimidation, ꢀwhichꢀisꢀalsoꢀanꢀelectrophilicꢀreaction.ꢀFu-
tureꢀstudiesꢀwillꢀfocusꢀonꢀunderstandingꢀthisꢀdifferenceꢀinꢀ
reactivity,ꢀ definingꢀ theꢀ detailedꢀ mechanismꢀ ofꢀ theꢀ C-Hꢀ
bondꢀ activationꢀ reactionꢀ (e.g.,ꢀ nitrogenꢀ reboundꢀ versusꢀ
nitrogenꢀnon-reboundꢀparallelꢀtoꢀoxygenꢀreactivityꢀinꢀnon-
IV
2+
4
6
c
1
30,ꢀ2716.ꢀ(e)ꢀSearles,ꢀK.;ꢀFortier,ꢀS.;ꢀKhusniyarov,ꢀM.ꢀM.;ꢀCarroll,ꢀ
12
hemeꢀ metal-oxoꢀ systems), ꢀ andꢀ understandingꢀ theꢀ reac-
P.ꢀ J.;ꢀ Sutter,ꢀ J.;ꢀ Meyer,ꢀ K.;ꢀ Mindiola,ꢀ D.ꢀ J.;ꢀ Caulton,ꢀ K.ꢀ G.ꢀ Angew.ꢀ
Chem.,ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ14139.ꢀ(f)ꢀHennessy,ꢀE.ꢀT.;ꢀBetley,ꢀT.ꢀA.ꢀ
Scienceꢀ2013,ꢀ340,ꢀ591.ꢀ(g)ꢀIovan,ꢀD.ꢀA.;ꢀBetley,ꢀT.ꢀA.ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.ꢀ 2016,ꢀ 138,ꢀ 1983.ꢀ (h)ꢀ Bucinsky,ꢀ L.;ꢀ Breza,ꢀ M.;ꢀ Lee,ꢀ W.-T.;ꢀ
Hickey,ꢀA.ꢀK.;ꢀDickie,ꢀD.ꢀA.;ꢀNeito,ꢀI.;ꢀDeGayner,ꢀJ.ꢀA.;ꢀHarris,ꢀT.ꢀD.;ꢀ
Meyer,ꢀ K.;ꢀ Krzystek,ꢀ J.;ꢀ Ozarowski,ꢀ A.;ꢀ Nehrkorn,ꢀ J.;ꢀ Schnegg,ꢀ A.;ꢀ
Holldack,ꢀ K.;ꢀ Herber.ꢀ R.ꢀ H.;ꢀ Telser,ꢀ J.;ꢀ Smith,ꢀ J.ꢀ M.ꢀ Inorg.ꢀ Chem.ꢀ
tivityꢀ differencesꢀ betweenꢀ nonhemeꢀ iron(V)-imidoꢀ com-
plexesꢀ andꢀ theirꢀ iron(V)-oxoꢀ analogsꢀ inꢀ C–Hꢀ bondꢀ activa-
tion,ꢀnitreneꢀgroupꢀversusꢀoxygenꢀatomꢀtransfer,ꢀandꢀelec-
tronꢀtransferꢀreactions.ꢀꢀ
ASSOCIATEDꢀCONTENTꢀꢀ
2
017,ꢀ56,ꢀ4751.ꢀ
SupportingꢀInformation.ꢀExperimentalꢀsection,ꢀTablesꢀS1ꢀ
5. Kaizer,ꢀ J.;ꢀ Klinker,ꢀ E.ꢀ J.;ꢀ Oh,ꢀ N.ꢀ Y.;ꢀ Rohde,ꢀ J.-U.;ꢀ Song,ꢀ W.ꢀ J.;ꢀ
Stubna,ꢀA.;ꢀKim,ꢀJ.;ꢀMünck,ꢀE.;ꢀNam,ꢀW.;ꢀQue,ꢀL.,ꢀJr.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ
2004,ꢀ126,ꢀ472.ꢀ
–
ꢀS6,ꢀandꢀFiguresꢀS1ꢀ–ꢀS24ꢀ(PDF).ꢀThisꢀmaterialꢀisꢀavailableꢀ
freeꢀofꢀchargeꢀviaꢀtheꢀInternetꢀatꢀhttp://pubs.acs.org.ꢀ
6
. (a)ꢀ Klinker,ꢀ E.ꢀ J.;ꢀ Jackson,ꢀ T.ꢀ A.;ꢀ Jensen,ꢀ M.ꢀ P.;ꢀ Stubna,ꢀ A.;ꢀ Ju-
hász,ꢀG.;ꢀBominaar,ꢀE.ꢀL.;ꢀMünck,ꢀE.;ꢀQue,ꢀL.,ꢀJr.ꢀAngew.ꢀChem.,ꢀInt.ꢀ
Ed.ꢀ2006,ꢀ45,ꢀ7394.ꢀ(b)ꢀVardhaman,ꢀA.ꢀK.;ꢀBarman,ꢀP.;ꢀKumar,ꢀS.;ꢀ
Sastri,ꢀC.ꢀV.;ꢀKumar,ꢀD.;ꢀdeꢀVisser,ꢀS.ꢀP.ꢀAngew.ꢀChem.,ꢀInt.ꢀEd.ꢀ2013,ꢀ
AUTHORꢀINFORMATIONꢀ
CorrespondingꢀAuthorꢀ
5
2,ꢀ12288.ꢀ(c)ꢀKumar,ꢀS.;ꢀFaponle,ꢀA.ꢀS.;ꢀBarman,ꢀP.;ꢀVardhaman,ꢀA.ꢀ
*
E-mail:ꢀwwnam@ewha.ac.kr;ꢀꢀ
K.;ꢀSastri,ꢀC.ꢀV.;ꢀKumar,ꢀD.;ꢀdeꢀVisser,ꢀS.ꢀP.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2014,ꢀ
136,ꢀ17102.ꢀ(d)ꢀVardhaman,ꢀA.ꢀK.;ꢀLee,ꢀY.-M.;ꢀJung,ꢀJ.;ꢀOhkubo,ꢀK.;ꢀ
Nam,ꢀW.;ꢀFukuzumi,ꢀS.ꢀAngew.ꢀChem.,ꢀInt.ꢀEd.ꢀ2016,ꢀ55,ꢀ3709.ꢀꢀ
edward.solomon@stanford.eduꢀ
AuthorꢀContributionsꢀ
7
.
(a)ꢀdeꢀOliveira,ꢀF.ꢀT.;ꢀChanda,ꢀA.;ꢀBanerjee,ꢀD.;ꢀShan,ꢀX.;ꢀMondal,ꢀ
S.;ꢀ Que,ꢀ L.,ꢀ Jr.;ꢀ Bominaar,ꢀ E.ꢀ L.;ꢀ Münck,ꢀ E.;ꢀ Collins,ꢀ T.ꢀ J.ꢀ Scienceꢀ
007,ꢀ315,ꢀ835.ꢀ(b)ꢀMills,ꢀM.ꢀR.;ꢀWeitz,ꢀA.ꢀC.;ꢀHendrich,ꢀM.ꢀP.;ꢀRy-
#ꢀS.H.ꢀandꢀK.D.S.ꢀcontributedꢀequallyꢀtoꢀthisꢀwork.ꢀꢀ
2
abov,ꢀ A.ꢀ D.;ꢀ Collins,ꢀ T.ꢀ J.ꢀ J.ꢀAm.ꢀChem.ꢀSoc.ꢀ2016,ꢀ 138,ꢀ 13866.ꢀ (c)ꢀ
Panda,ꢀC.;ꢀDebgupta,ꢀJ.;ꢀDíazꢀD.ꢀD.;ꢀSingh,ꢀK.ꢀK.;ꢀGupta,ꢀS.ꢀS.;ꢀDhar,ꢀB.ꢀ
B.ꢀ J.ꢀAm.ꢀChem.ꢀSoc.ꢀ 2014,ꢀ 136,ꢀ 12273.ꢀ (d)ꢀ Kwon,ꢀ E.;ꢀ Cho,ꢀ K.-B.;ꢀ
Hong,ꢀS.;ꢀNam,ꢀW.ꢀChem.ꢀCommun.ꢀ2014,ꢀ50,ꢀ5572.ꢀ
Noteꢀ
Theꢀauthorsꢀdeclareꢀnoꢀcompetingꢀfinancialꢀinterest.ꢀ
ACKNOWLEDGMENTꢀꢀ
8
.
deꢀVisser,ꢀS.ꢀP.;ꢀRohde,ꢀJ.-U.;ꢀLee,ꢀY.-M.;ꢀCho,ꢀJ.;ꢀNam,ꢀW.ꢀCoord.ꢀ
Chem.ꢀRev.ꢀ2013,ꢀ257,ꢀ381.ꢀ
Mehn,ꢀM.ꢀP.;ꢀBrown,ꢀS.ꢀD.;ꢀJenkins,ꢀD.ꢀM.;ꢀPeters,ꢀJ.ꢀC.;ꢀQue,ꢀL.,ꢀJr.ꢀ
Thisꢀ workꢀ wasꢀ supportedꢀ byꢀ NRFꢀ ofꢀ Koreaꢀ throughꢀ CRIꢀ
9
.
(
0
NRF-2012R1A3A2048842ꢀ toꢀ W.N.),ꢀ GRLꢀ (NRF-2010-
0353ꢀ toꢀ W.N.),ꢀ MSIPꢀ (NRF-2017R1C1B2002037ꢀ toꢀ S.H.),ꢀ
Inorg.ꢀChem.ꢀ2006,ꢀ45,ꢀ7417.ꢀ
10. Itꢀisꢀworthꢀnotingꢀthatꢀiron-nitridoꢀcomplexesꢀexhibitedꢀFe-Nꢀ
vibrationalꢀenergyꢀatꢀ~860ꢀ–ꢀ1100ꢀcm–1.ꢀ
11. Gorelsky,ꢀ S.ꢀ I.;ꢀ Basumallick,ꢀ L.;ꢀ Vura-Weis,ꢀ J.;ꢀ Sarangi,ꢀ R.;ꢀ
Hodgson,ꢀ K.ꢀ O.;ꢀ Hedman,ꢀ B.;ꢀ Fujisawa,ꢀ K.;ꢀ Solomon,ꢀ E.ꢀ I.ꢀ Inorg.ꢀ
Chem.ꢀ2005,ꢀ44,ꢀ4947.ꢀ
andꢀSookmyungꢀWomen’sꢀUniversityꢀGrantsꢀ(1-1603-2054ꢀ
toꢀ S.H.).ꢀ Fundingꢀ forꢀ thisꢀ workꢀ wasꢀ alsoꢀ providedꢀ byꢀ theꢀ
NIHꢀ(GM-40392ꢀtoꢀE.I.S.).ꢀT.O.ꢀacknowledgesꢀtheꢀsupportꢀofꢀ
“
Strategicꢀ Youngꢀ Researcherꢀ Overseasꢀ Visitsꢀ Programꢀforꢀ
1
2. Cho,ꢀK.-B.;ꢀHirao,ꢀH.;ꢀShaik,ꢀS.;ꢀNam,ꢀW.ꢀChem.ꢀSoc.ꢀRev.ꢀ2016,ꢀ
AcceleratingꢀBrainꢀCirculation”ꢀandꢀGrant-in-AidꢀforꢀScien-
tificꢀ Researchꢀ(No.ꢀ 15H00960)ꢀ byꢀ JSPS.ꢀ Useꢀ ofꢀ theꢀ SSRL,ꢀ
45,ꢀ1197.ꢀꢀ
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