[RuCl2(η6-p-cymene)] complexes bearing phosphinous acid ligands: Preparation, application in C-H bond functionalization and mechanistic investigations

Article abstract of DOI:10.1039/c5dt04683a

A series of [RuCl₂(η⁶-p-cymene)] complexes bearing phosphinous acid (PA) ligands have been straightforwardly prepared from the dimer [RuCl₂(p-cymene)]₂ and secondary phosphine oxides (SPOs) and fully characteriz

Full text of DOI:10.1039/c5dt04683a

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: L. V. Graux, M.
Giorgi, G. Buono and H. CLAVIER, Dalton Trans., 2016, DOI: 10.1039/C5DT04683A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/dalton

Page 1 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
View Article Online
DOI: 10.1039/C5DT04683A
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
6
ꢀ
[
RuCl (η ‐p-cymene)] complexesꢀbearingꢀphosphinousꢀacidꢀ
2
ligands:ꢀꢀpreparation,ꢀapplicationꢀinꢀC-Hꢀbondꢀfunctionalizationꢀ
andꢀmechanisticꢀinvestigationsꢀ
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
a
b
a
a*ꢀ
LionelꢀV.ꢀGraux, ꢀMichelꢀGiorgi, ꢀGérardꢀBuono ꢀandꢀHervéꢀClavier
6
ꢀ
Aꢀseriesꢀofꢀ[RuCl
2
(η ‐p-cymene)] complexesꢀbearingꢀphosphinousꢀacidꢀ(PA)ꢀligandsꢀhasꢀbeenꢀstraightforwardlyꢀpreparedꢀ
fromꢀtheꢀdimerꢀ[RuCl
2
(p-cymene)]
2
ꢀandꢀsecondaryꢀphosphineꢀoxidesꢀ(SPOs),ꢀandꢀfullyꢀcharacterized.ꢀTheꢀstericꢀparameterꢀ
6
quantificationꢀofꢀPAs,ꢀotherꢀLꢀligandsꢀandꢀη ‐p-cymeneꢀallowedꢀaꢀbetterꢀcomprehensionꢀofꢀtheꢀcoordinationꢀchemistryꢀofꢀ
thisꢀ typeꢀ ofꢀ complexesꢀ andꢀ explainedꢀ theꢀ absenceꢀ ofꢀ coordinationꢀ inꢀ theꢀ caseꢀ ofꢀ bulkyꢀ SPOsꢀ suchꢀ asꢀ Ad
complexesꢀwereꢀtestedꢀinꢀtheꢀC-Hꢀactivation/functionalizationꢀofꢀ2-phenylpyridineꢀandꢀaꢀgoodꢀactivityꢀwasꢀobtainedꢀatꢀ80ꢀ
Cꢀforꢀtheꢀcomplexꢀexhibitingꢀtheꢀhighestꢀstericꢀbulk.ꢀAꢀstudyꢀonꢀhalideꢀeffects,ꢀeitherꢀonꢀtheꢀrutheniumꢀcomplexꢀorꢀforꢀtheꢀ
2
P(O)H.ꢀ Theseꢀ
°
arylꢀhalideꢀpartner,ꢀhasꢀalsoꢀbeenꢀcarriedꢀoutꢀandꢀshowedꢀdrasticꢀdifferences.ꢀFurtherꢀinvestigationsꢀonꢀhalidesꢀeffectsꢀ
wereꢀperformedꢀnotablyꢀusingꢀcationicꢀruthenacycleꢀwhichꢀwasꢀfoundꢀtoꢀbeꢀanꢀintermedaiteꢀofꢀtheꢀreaction.ꢀInꢀorderꢀtoꢀ
rationalizeꢀtheꢀroleꢀplayedꢀbyꢀtheꢀphosphinousꢀacid,ꢀaꢀmechanismꢀinvolvingꢀaꢀconcertedꢀmetallationꢀdeprotonationꢀfavoredꢀ
byꢀ
aꢀ
phosphinitoꢀ
speciesꢀ
hasꢀ
beenꢀ
proposed.ꢀꢀ
13
wereꢀachievedꢀusingꢀRu-basedꢀcomplexes, ꢀcatalyticꢀsystemsꢀ
usingꢀPdꢀorꢀRhꢀhaveꢀattractedꢀmuchꢀattentionꢀduringꢀtheꢀlastꢀ
decade.ꢀ Nevertheless,ꢀ interestingꢀ Ru-basedꢀ catalyticꢀ systemsꢀ
haveꢀ beenꢀ reportedꢀ inꢀ theꢀ literatureꢀ mainlyꢀ usingꢀ theꢀ dimerꢀ
Introductionꢀ
Consideredꢀ forꢀ aꢀ longꢀ timeꢀ asꢀ aꢀ mainꢀ challengeꢀ inꢀ organicꢀ
synthesis,ꢀ theꢀ C-Hꢀ activation/functionalizationꢀ hasꢀ emergedꢀ
recentlyꢀ asꢀ aꢀ powerfulꢀ toolꢀ toꢀ prepareꢀ complexꢀ moleculesꢀ
[
RuCl2(p-cymene)]2ꢀ inꢀ associationꢀ withꢀ carboxylateꢀ
4,14
1
additives. ꢀ Ourꢀ researchꢀ involvingꢀ secondaryꢀ phosphineꢀ
oxidesꢀ (SPO)ꢀ andꢀ phosphinousꢀ acidsꢀ (PA)ꢀ asꢀ ligandsꢀ inꢀ
startingꢀfromꢀreadilyꢀavailableꢀrawꢀmaterials. ꢀInꢀthisꢀquest,ꢀtheꢀ
useꢀ ofꢀ transitionꢀ metalꢀ catalysisꢀ isꢀ atꢀ theꢀ originꢀ ofꢀ
groundbreakingꢀdiscoveriesꢀandꢀnowꢀvariousꢀcatalyticꢀsystemsꢀ
15
transitionꢀmetalꢀcatalysis, ꢀtheꢀcatalyticꢀsystemꢀusingꢀ[RuCl2(p-
2
3
4
5
6
usingꢀ palladium, ꢀ rhodium, ꢀ ruthenium, ꢀ copper, ꢀ platinum, ꢀ
cymene)]2ꢀandꢀSPOꢀdevelopedꢀbyꢀAckermannꢀinꢀ2005ꢀcaughtꢀ
16
7
8
9
ourꢀattentionꢀ(Schemeꢀ1). ꢀAꢀRu(II)ꢀcomplex,ꢀpreparedꢀinꢀsituꢀ
6
fromꢀ [RuCl2(η -p-cymene)]2ꢀ andꢀ stericallyꢀ hinderedꢀ
nickel, ꢀ cobalt, ꢀ f-blockꢀ elements, ꢀ etcꢀ areꢀ recognizedꢀ toꢀ beꢀ
highlyꢀ efficientꢀ forꢀ C-Hꢀ bondꢀ activation.ꢀ Inꢀ theseꢀ systems,ꢀ
majorꢀ advancesꢀ wereꢀ accomplishedꢀ byꢀ clearꢀ mechanisticꢀ
studiesꢀ whichꢀ allowedꢀ deeperꢀ understandingꢀ ofꢀ theꢀ
mechanism,ꢀ notablyꢀ theꢀ roleꢀ ofꢀ ligandsꢀ and/orꢀ additives.ꢀ Forꢀ
instance,ꢀCatellaniꢀdevelopedꢀaꢀPd-catalyzedꢀregioselectiveꢀC-Hꢀ
bondꢀ functionalizationꢀ ofꢀ arenesꢀ usingꢀ norborneneꢀ asꢀ aꢀ
diadamantylphosphineꢀ oxide,ꢀ wasꢀ foundꢀ veryꢀ efficientꢀ forꢀ
orthoꢀ C-Hꢀ bondꢀ activationꢀ ofꢀ theꢀ 2-phenylpyridineꢀ 1ꢀ andꢀ
couplingꢀwithꢀchlorobenzeneꢀtoꢀyieldꢀquantitativelyꢀcompoundꢀ
3
ꢀ withoutꢀ anyꢀ tracesꢀ ofꢀ monoarylatedꢀ 2.ꢀ Moreover,ꢀ thisꢀ
catalyticꢀ systemꢀ showedꢀ aꢀ highꢀ efficiencyꢀ forꢀ variousꢀ
17
10
substrates. ꢀWeꢀwonderedꢀaboutꢀtheꢀroleꢀplayedꢀbyꢀtheꢀSPOꢀ
orꢀitsꢀtautomericꢀphosphinousꢀacidꢀformꢀinꢀtheꢀC-Hꢀactivationꢀ
process.ꢀ Whereasꢀ severalꢀ mechanisticꢀ hypothesisꢀ haveꢀ beenꢀ
covalentꢀlinker. ꢀAlternatively,ꢀitꢀwasꢀdemonstratedꢀthatꢀC-Hꢀ
activationꢀ couldꢀ occurꢀ accordingꢀ toꢀ aꢀ σ-bondꢀ metathesisꢀ
11
pathway, ꢀ soꢀ calledꢀ concertedꢀ metallationꢀ deprotonationꢀ
(CMD).ꢀInꢀsuchꢀprocess,ꢀtheꢀintermolecularꢀabstractionꢀofꢀtheꢀ
protonꢀbyꢀacetatoꢀligandsꢀfavorsꢀtheꢀmetallacycleꢀformation. ꢀꢀ
4,17c
postulated, ꢀnoneꢀofꢀthemꢀwasꢀfurtherꢀinvestigated.ꢀꢀ
Therefore,ꢀweꢀwishedꢀtoꢀinvestigateꢀtheꢀmechanismꢀofꢀthisꢀC-Hꢀ
bondꢀ activation/functionalizationꢀ throughꢀ theꢀ synthesisꢀ ofꢀ
12
2
Whereasꢀ pioneeringꢀ worksꢀ onꢀ catalyticꢀ C(sp )-Hꢀ activationꢀ
6
well-definedꢀ[RuCl2(η ‐p‐cymene)(PA)]ꢀcomplexesꢀandꢀtheꢀꢀ
Ph-Cl
[RuCl2(p-cymene)]2 (2.5 mol%)
Ph
Ph
Ad2P(O)H (10 mol%)
N
N
N
K2CO3, NMP, 120 °C, 24 h
Ph
3 (95%)
1
2 (not detected)
ꢀ
Schemeꢀ1ꢀC-Hꢀactivation/functionalizationꢀmediatedꢀbyꢀRuCl
2
(p-cymene)]2ꢀandꢀSPO.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
Page 2 of 11
ARTICLEꢀ
JournalꢀNameꢀ
3
1
1
a
Tableꢀ2ꢀ P{ H}ꢀNMRꢀspectralꢀdataꢀforꢀSPOsꢀ4ꢀandꢀRu-complexesꢀ5. ꢀ
studyꢀofꢀtheirꢀperformancesꢀinꢀcatalysis.ꢀControlꢀexperimentsꢀ
haveꢀ beenꢀ carriedꢀ outꢀ toꢀ corroborateꢀ mechanisticꢀ proposal.ꢀ
Theꢀresultsꢀofꢀourꢀstudyꢀareꢀreportedꢀtherein.ꢀ
View Article Online
DOI: 10.1039/C5DT04683A
31
1
31
1
Entryꢀ
SPOꢀ
4bꢀ
4cꢀ
4dꢀ
4eꢀ
4hꢀ
4iꢀ
P{ H}ꢀ(ppm)ꢀ
Complexꢀ5ꢀ
P{ H}ꢀ(ppm)ꢀ
1
2
3
4
5
6
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
50.0ꢀ
21.4ꢀ
18.2ꢀ
22.8ꢀ
20.2ꢀ
28.0ꢀ
29.6ꢀ
36.7ꢀ
47.4ꢀ
5bꢀ
5cꢀ
5dꢀ
5eꢀ
5hꢀ
5iꢀ
129.3ꢀ
107.1ꢀ
105.6ꢀ
107.0ꢀ
109.5ꢀ
113.1ꢀ
109.4ꢀ
114.2ꢀ
115.5ꢀ
Resultsꢀandꢀdiscussionꢀ
WeꢀstartedꢀtoꢀstudyꢀtheꢀcoordinationꢀchemistryꢀofꢀSPOsꢀwithꢀ
6
RuCl2(p-cymene)]2.ꢀTheꢀsynthesisꢀofꢀ[RuCl2(η ‐arene)(PA)]ꢀhasꢀ
[
beenꢀ previouslyꢀ reportedꢀ inꢀ theꢀ literature, ꢀ notablyꢀ twoꢀ
18
7ꢀ
8ꢀ
4jꢀ
5jꢀ
6
complexesꢀ [Ru(η ‐p‐cymene)Cl2(PA)]ꢀ 5aꢀ andꢀ 5lꢀ wereꢀ alreadyꢀ
4kꢀ
4lꢀ
5kꢀ
5lꢀ
19
20
describedꢀ byꢀ theꢀ groupsꢀ ofꢀ Tyler ꢀ andꢀ Leung ꢀ respectivelyꢀ
9ꢀ
a
ꢀ
ꢀ
3
MeasuredꢀinꢀCDCl ꢀatꢀ25ꢀ°C.
(
hydratation.
Fig.ꢀ 1)ꢀ andꢀ 5aꢀ hasꢀ beenꢀ successfullyꢀ appliedꢀ toꢀ nitrileꢀ
ꢀꢀ
19,21
asꢀ massꢀ spectrometry.ꢀ Theꢀ coordinationꢀ ofꢀ theꢀ phosphinousꢀ
acidꢀtoꢀtheꢀmetallicꢀcenterꢀthroughꢀtheꢀphosphorusꢀatomꢀwasꢀ
Followingꢀtheꢀsameꢀprocedure,ꢀ[RuCl2(p-cymene)]2ꢀwasꢀtreatedꢀ
withꢀvariousꢀsecondaryꢀphosphineꢀoxidesꢀ4ꢀinꢀTHFꢀatꢀ25ꢀ°Cꢀtoꢀ
1
confirmedꢀbyꢀNMRꢀspectroscopiesꢀandꢀtheꢀabsenceꢀofꢀ J(P,H)ꢀ
22
affordꢀ theꢀ expectedꢀ complexesꢀ 5ꢀ (Tableꢀ 1). ꢀ Ofꢀ note,ꢀ inꢀ
dichloromethaneꢀ orꢀ toluene,ꢀ theꢀ reactionꢀ wasꢀ sluggishꢀ
comparedꢀtoꢀTHF.ꢀExpectedꢀforꢀCy2P(O)Hꢀ4bꢀwhichꢀrequiredꢀ24ꢀ
hꢀofꢀreaction,ꢀotherꢀSPOs,ꢀeitherꢀsymmetricalꢀonesꢀ(entriesꢀ2-4)ꢀ
orꢀ unsymmetricalꢀ onesꢀ (entriesꢀ 7-11),ꢀ wereꢀ foundꢀ veryꢀ
reactive.ꢀAfterꢀonlyꢀ2-3ꢀh,ꢀcomplexesꢀ5ꢀwereꢀisolatedꢀinꢀalmostꢀ
quantitativeꢀ yields.ꢀ Surprisingly,ꢀ withꢀ bulkyꢀ SPOsꢀ suchꢀ asꢀ
Ad2P(O)Hꢀ 4fꢀ orꢀ tBu2P(O)Hꢀ 4g,ꢀ weꢀ wereꢀ unableꢀ toꢀ obtainꢀ theꢀ
correspondingꢀ complexesꢀ 5ꢀ (entriesꢀ 5ꢀ andꢀ 6).ꢀ Despiteꢀ
prolongedꢀ reactionꢀ timesꢀ and/orꢀ heatingꢀ toꢀ 110ꢀ °C,ꢀ theirꢀ
formationꢀcouldꢀnotꢀbeꢀdetectedꢀbyꢀNMRꢀspectroscopy.ꢀꢀ
31
coupling.ꢀ Moreover,ꢀ Pꢀ NMRꢀ spectroscopiesꢀ showedꢀ newꢀ
resonancesꢀ betweenꢀ 105-130ꢀ ppmꢀ withꢀ aꢀ significantꢀ shiftꢀ toꢀ
lowerꢀ fieldꢀ comparedꢀ toꢀ SPOsꢀ (Δδꢀ betweenꢀ 68ꢀ andꢀ 89ꢀ ppm,ꢀ
Tableꢀ2).ꢀꢀ
6
Toꢀ establishꢀ unambiguouslyꢀ theꢀ structureꢀ ofꢀ [RuCl2(η -p-
cymene)(PA)]ꢀ complexesꢀ 5,ꢀ suitableꢀ crystalsꢀ forꢀ single-crystalꢀ
X-rayꢀ diffractionꢀ studiesꢀ wereꢀ obtainedꢀ forꢀ mostꢀ ofꢀ theꢀ
compounds.ꢀ Asꢀ depictedꢀ inꢀ Fig.ꢀ 2,ꢀ allꢀ complexesꢀ adoptꢀ aꢀ
distortedꢀoctahedralꢀstructureꢀwithꢀtheꢀexpectedꢀthree-leggedꢀ
pseudotetrahedralꢀ “piano-stool”ꢀ geometryꢀ aroundꢀ theꢀ Ruꢀ
6
atomꢀandꢀtheꢀη -coordinationꢀofꢀtheꢀp-cymene.ꢀTwoꢀchlorineꢀ
6
Theꢀ well-definedꢀ [RuCl2(η ‐p‐cymene)(PA)]ꢀ 5ꢀ wereꢀ
23 13
characterizedꢀbyꢀ H, ꢀ C,ꢀandꢀ PꢀNMRꢀspectroscopy,ꢀasꢀwellꢀꢀ
atomsꢀandꢀtheꢀphosphorusꢀoccupyꢀtheꢀotherꢀthreeꢀpositions.ꢀ
Bondꢀ lengthsꢀ areꢀ similarꢀ toꢀ thoseꢀ reportedꢀ forꢀ analogousꢀ
complexesꢀ (Tableꢀ 3);ꢀ theꢀ Ru-Clꢀ bondꢀ distancesꢀ rangeꢀ fromꢀ
2.3943(10)ꢀ toꢀ 2.4395(7)ꢀ Å,ꢀ theꢀ Ru-Pꢀ bondꢀ lengthsꢀ fromꢀ
1
31
Me
iPr
OH
Me
iPr
OH
2
.3009(8)ꢀtoꢀ2.3680(7)ꢀÅꢀandꢀtheꢀlongestꢀdistancesꢀhaveꢀbeenꢀ
observedꢀwithꢀcyclohexylꢀandꢀtert-butylꢀP-substituentsꢀ(entriesꢀ
,ꢀ 6ꢀ andꢀ 7).ꢀ Thisꢀ seemsꢀ toꢀ beꢀ theꢀ resultꢀ ofꢀ aꢀ higherꢀ stericꢀ
congestionꢀ ofꢀ PAꢀ ligands.ꢀ Theꢀ P-Oꢀ bondꢀ lengthsꢀ (allꢀ closeꢀ toꢀ
.60ꢀ Å)ꢀ areꢀ consistentꢀ withꢀ aꢀ P-Oꢀ singleꢀ bond.ꢀ Theꢀ O···Clꢀ
distancesꢀrangingꢀfromꢀ2.961(2)ꢀtoꢀ3.070(2)ꢀÅꢀ–ꢀexceptꢀforꢀ5h,ꢀ
.175(2)ꢀ Å,ꢀ entryꢀ 4ꢀ –ꢀ indicateꢀ anꢀ hydrogenꢀ bondingꢀ withꢀ
Cl Ru
Cl
Cl Ru
Cl
P
P
Me
Ph
tBu
Me
1
5
a
5l
ꢀ
6
Fig.ꢀ1ꢀ[RuCl
2
(η ‐p‐cymene)(PA)]ꢀcomplexesꢀdescribedꢀinꢀtheꢀliterature.ꢀ
1
6
a
Tableꢀ1ꢀPreparationꢀofꢀwell-definedꢀ[RuCl
2
(η -p-cymene)(PA)]ꢀcomplexes. ꢀ
3
chlorines.ꢀOfꢀnote,ꢀwithꢀ5h,ꢀtheꢀhydrogenꢀbondingꢀtakesꢀplaceꢀ
intermolecularly.ꢀꢀ
Me
iPr
OH
O
[
RuCl2(p-cymene)]2
P
R1
Cl Ru
Cl
Inꢀorderꢀtoꢀgainꢀmoreꢀinsightsꢀontoꢀtheꢀcoordinationꢀchemistryꢀ
ofꢀ[RuCl2(p-cymene)(L)]ꢀandꢀparticularlyꢀtoꢀaddressꢀtheꢀissueꢀofꢀ
absenceꢀofꢀreactionꢀwithꢀbulkyꢀSPOsꢀAd2P(O)Hꢀ4fꢀorꢀtBu2P(O)Hꢀ
4g,ꢀ weꢀ quantifiedꢀ theꢀ stericꢀ parameterꢀ ofꢀ phosphinousꢀ acidsꢀ
andꢀotherꢀligandsꢀLꢀ(phosphine,ꢀphosphiteꢀandꢀN-heterocyclicꢀ
H
R2
THF, 25 °C
R2
P
R1
4
b-l
5b-l
ꢀ
1
2
R ꢀ
Entryꢀ
R ꢀ
Cyꢀ
Phꢀ
tꢀ(h)ꢀ
Complexꢀ Yieldꢀ(%)ꢀ
1
2
3
4
ꢀ
ꢀ
ꢀ
ꢀ
Cyꢀ
Phꢀ
24ꢀ
2ꢀ
5bꢀ
5cꢀ
5dꢀ
5eꢀ
5fꢀ
5gꢀ
5hꢀ
5iꢀ
89ꢀ
96ꢀ
84ꢀ
91ꢀ
NRꢀ
NRꢀ
74ꢀ
53ꢀ
88ꢀ
98ꢀ
99ꢀ
2
4,25
carbeneꢀ(NHC))ꢀthroughꢀtheꢀpercentꢀburiedꢀvolumeꢀ(%Vbur).
ꢀ
p-F-C
3,5-Me
6
H
4
ꢀ
p-F-C
3,5-Me
Adꢀ
6
H
4
ꢀ
6ꢀ
23
Selectedꢀvaluesꢀhaveꢀbeenꢀgatheredꢀinꢀtableꢀ4. ꢀTheꢀ%Vburꢀforꢀ
PAꢀ ligandsꢀ spanꢀ fromꢀ 21.9ꢀ toꢀ 24.6%.ꢀ Theseꢀ valuesꢀ areꢀ
significantlyꢀ lowerꢀ thanꢀ thoseꢀ calculatedꢀ onꢀ AuCl(PA)ꢀ
2
-C
6
H
3
ꢀ
2
-C
6
H
3
ꢀ
3ꢀ
b
5
6
ꢀ
ꢀ
Adꢀ
tBuꢀ
Meꢀ
nBuꢀ
Bnꢀ
24ꢀ
24ꢀ
3ꢀ
b
tBuꢀ
Phꢀ
Phꢀ
Phꢀ
Phꢀ
Phꢀ
15g
complexes. ꢀ Asꢀ expectedꢀ Ph2POHꢀ isꢀ moreꢀ stericallyꢀ
demandingꢀ thanꢀ Ph2PHꢀ (entriesꢀ 3ꢀ andꢀ 9)ꢀ butꢀ lessꢀ thanꢀ
Ph2PCH2OH,ꢀ Ph2PnBu,ꢀ PPh3ꢀ orꢀ P(OPh)3ꢀ (entriesꢀ 9-13).ꢀ Theꢀ
highestꢀ%Vburꢀcalculatedꢀinꢀ[RuCl2(p-cymene)(L)]ꢀcomplexesꢀisꢀ
forꢀ theꢀ NHCꢀ IMesꢀ (1,3-dimesityl-imidazol-2-ylidene)ꢀ (27.9%)ꢀ
7
ꢀ
8
9
ꢀ
ꢀ
3ꢀ
3ꢀ
5jꢀ
1
1
0ꢀ
1ꢀ
Cyꢀ
3ꢀ
5kꢀ
5lꢀ
tBuꢀ
3ꢀ
24
whichꢀisꢀinꢀtheꢀlowerꢀrangeꢀforꢀthisꢀligandꢀ(entryꢀ14). ꢀTheseꢀ
lowꢀ%Vburꢀvaluesꢀandꢀtheirꢀnarrowꢀrangeꢀattestꢀprobablyꢀthatꢀ
theꢀotherꢀligandsꢀꢀ
a
b
6
ꢀ
ꢀ
2 2
Reactionꢀconditions:ꢀ[RuCl (η -p-cymene)] ,ꢀSPOꢀ(2.2ꢀequiv.),ꢀTHFꢀ(0.5M),ꢀ25ꢀ°C.ꢀ
reactionꢀperformedꢀinꢀ1,4-dioxaneꢀatꢀ110ꢀ°C.ꢀNRꢀ=ꢀNoꢀreaction.ꢀꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 3 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
View Article Online
DOI: 10.1039/C5DT04683A
JournalꢀNameꢀ
ARTICLEꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ ꢀ
ꢀ
ꢀ
5bꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5cꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5dꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5
hꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5iꢀ
ꢀ
ꢀ
ꢀ
Fig.ꢀ2ꢀMolecularꢀstructuresꢀofꢀcomplexesꢀ5b-d,ꢀ5h-iꢀandꢀ5k-lꢀrepresentedꢀatꢀ50%ꢀellipsoidꢀprobability.ꢀMostꢀofꢀtheꢀHꢀatomsꢀhaveꢀbeenꢀomittedꢀforꢀclarity.ꢀꢀ
5kꢀ
ꢀ
ꢀ
ꢀ
5lꢀ
ꢀ
Tableꢀ3ꢀSelectedꢀbondꢀlengthsꢀ(Å)ꢀforꢀcomplexesꢀ[RuCl (p-cymene)(PA)]ꢀ5b-d,ꢀ5h-iꢀandꢀ5k-l.ꢀ
2
ꢀ
Entryꢀ
Complexꢀ
Ru(1)-Cl(1)ꢀ(Å)ꢀ
.4323(10)ꢀ
2.4320(10)ꢀ
.4296(10)ꢀ
Ru(1)-Cl(2)ꢀ(Å)ꢀ
2.3943(10)ꢀ
2.4198(9)ꢀ
2.4072(9)ꢀ
2.4156(8)ꢀ
2.3970(8)ꢀ
2.4197(6)ꢀ
2.4032(11)ꢀ
2.4389(9)ꢀ
2.4124(7)ꢀ
Ru(1)-P(1)ꢀ(Å)ꢀ
2.3376(9)ꢀ
2.3379(9)ꢀ
2.3445(10)ꢀ
2.3120(8)ꢀ
2.3009(8)ꢀ
2.3130(6)ꢀ
2.3017(10)ꢀ
2.3342(8)ꢀ
2.3680(7)ꢀ
P(1)-O(1)ꢀ(Å)ꢀ
1.600(3)ꢀ
O···Clꢀ(Å)ꢀ
2.988(3)ꢀ
3.005(3)ꢀ
3.027(3)ꢀ
3.070(2)ꢀ
3.011(3)ꢀ
3.175(2)ꢀ
2.988(3)ꢀ
3.009(2)ꢀ
2.961(2)ꢀ
Ru(1)-Cavgꢀ(Å)ꢀ
2.203(4)ꢀ
2.214(4)ꢀ
2.215(4)ꢀ
2.216(3)ꢀ
2.212(3)ꢀ
2.210(3)ꢀ
2.209(4)ꢀ
2.212(3)ꢀ
2.214(3)ꢀ
2
1
ꢀ
5bꢀ
1.602(3)ꢀ
2
1.612(3)ꢀ
2
3
4
5
6
7
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
5cꢀ
5dꢀ
5hꢀ
5iꢀ
2.4171(8)ꢀ
2.4147(9)ꢀ
2.4024(6)ꢀ
2.4295(11)ꢀ
2.3966(8)ꢀ
2.4395(7)ꢀ
1.602(2)ꢀ
1.605(2)ꢀ
1.6034(19)ꢀ
1.604(3)ꢀ
5kꢀ
5lꢀ
1.601(2)ꢀ
1.6098(19)ꢀ
ꢀ
inꢀtheꢀcoordinationꢀsphereꢀofꢀtheꢀRuꢀareꢀstericallyꢀdemandingꢀ Aꢀ controlꢀ experimentꢀ showedꢀ thatꢀ atꢀ 120ꢀ °C,ꢀ [RuCl2(p-
andꢀtheꢀLꢀligandꢀhasꢀthereforeꢀtoꢀminimizeꢀitsꢀsize.ꢀTheꢀ%Vburꢀofꢀ cymene)]2ꢀ withoutꢀ additionꢀ ofꢀ SPOꢀ wasꢀ competentꢀ forꢀ C-Hꢀ
6
theꢀ η -p-cymeneꢀ hasꢀ beenꢀ alsoꢀ quantifiedꢀ inꢀ 24ꢀ X-rayꢀ functionalizationꢀ sinceꢀ 88%ꢀ ofꢀ diarylatedꢀ productꢀ 3ꢀ wasꢀ
structuresꢀ andꢀ theꢀ sizeꢀ ofꢀ thisꢀ ligandꢀ wasꢀ foundꢀ relativelyꢀ isolatedꢀ(entryꢀ1).ꢀAtꢀ100°C,ꢀonlyꢀminuteꢀamountsꢀofꢀproductsꢀ
invariantꢀ withꢀ anꢀ averageꢀ valueꢀ ofꢀ 47.5%ꢀ andꢀ aꢀ standardꢀ 2ꢀ andꢀ 3ꢀ wereꢀ obtainedꢀ withꢀ [RuCl2(p-cymene)]2ꢀ (entryꢀ 2)ꢀ
23ꢀ
6
deviationꢀofꢀ0.35%. Asꢀintuitivelyꢀexpected,ꢀtheꢀη -p-cymeneꢀ whereasꢀaddingꢀeitherꢀ5ꢀotherꢀ10ꢀmol%ꢀofꢀAd2POHꢀallowedꢀtoꢀ
occupiesꢀalmostꢀhalfꢀofꢀtheꢀRuꢀcoordinationꢀsphereꢀandꢀdoesꢀ isolatedꢀaroundꢀ80%ꢀofꢀdiarylatedꢀproductꢀ3ꢀ(entriesꢀ3ꢀandꢀ4).ꢀ
notꢀ showꢀ anyꢀ structuralꢀ flexibilities.ꢀ Therefore,ꢀ theꢀ However,ꢀ loweringꢀ theꢀ reactionꢀ temperatureꢀ toꢀ 80ꢀ °Cꢀ ledꢀ toꢀ
coordinationꢀofꢀstericallyꢀhinderedꢀligands,ꢀsuchꢀasꢀAd2POHꢀorꢀ theꢀlossꢀofꢀactivityꢀofꢀtheꢀdimerꢀ[RuCl2(p-cymene)]2ꢀ(entryꢀ5).ꢀInꢀ
tBu2POH,ꢀ seemsꢀ unlikely.ꢀ Indeed,ꢀ calculationsꢀ performedꢀ onꢀ oneꢀ hand,ꢀ atꢀ thisꢀ temperature,ꢀ [RuCl2(p-cymene)]2ꢀ inꢀ
otherꢀcomplexesꢀshownꢀthatꢀ%VburꢀofꢀtBu2POHꢀandꢀAd2POHꢀareꢀ associationꢀwithꢀAd2P(O)Hꢀ4fꢀgaveꢀonlyꢀsmallꢀamountsꢀofꢀ2ꢀandꢀ
2
3
6
aroundꢀ30.5ꢀandꢀ31.5,ꢀrespectively. ꢀ
3ꢀ (entryꢀ 6).ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ well-definedꢀ [RuCl2(η ‐
6
Havingꢀ preparedꢀ aꢀ seriesꢀ ofꢀ well-definedꢀ [RuCl2(η ‐ cymene)(PA)]ꢀ5a-eꢀandꢀ5i-kꢀwereꢀfoundꢀmuchꢀmoreꢀcompetentꢀ
cymene)(PA)],ꢀ weꢀ haveꢀ thenꢀ testedꢀ theirꢀ catalyticꢀ andꢀsignificantꢀquantitiesꢀofꢀC-Hꢀfunctionalizedꢀproductsꢀwereꢀ
performancesꢀ inꢀ C-Hꢀ activationꢀ usingꢀ 2-phenylpyridineꢀ 1ꢀ asꢀ isolatedꢀ (entriesꢀ 7-14).ꢀ Sinceꢀ reactionsꢀ didꢀ notꢀ reachꢀ
benchmarkꢀsubstrateꢀusingꢀAckermann’sꢀconditionsꢀ(Tableꢀ5).ꢀ completion,ꢀca.ꢀ1:1ꢀmixturesꢀofꢀmono-ꢀandꢀdiarylatedꢀproductsꢀꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
Page 4 of 11
ARTICLEꢀ
JournalꢀNameꢀ
6
Tableꢀ 4ꢀ Percentꢀ ofꢀ buriedꢀ volumeꢀ ofꢀ variousꢀ ligandsꢀ Lꢀ inꢀ [RuCl
2
(η ‐p‐cymene)(L)]ꢀ
5
lꢀ (entryꢀ 17).ꢀ Theꢀ electronicꢀ propertiesꢀ ofꢀ phospVhieiwnAoruticsleꢀ aOcnildinesꢀ
a
complexes. ꢀ
DOI: 10.1039/C5DT04683A
didꢀ notꢀ influenceꢀ theꢀ catalyticꢀ activitiesꢀ ofꢀ theꢀ resultingꢀ
complexes.ꢀ Forꢀ exampleꢀ Ph2POH-containingꢀ 5cꢀ performedꢀ
betterꢀ thanꢀ 5bꢀ bearingꢀ theꢀ moreꢀ electronꢀ richꢀ Cy2POHꢀ andꢀ
thanꢀ 5dꢀ bearingꢀ electronꢀ withdrawingꢀ ligandꢀ (p-F-C6H4)2POHꢀ
(entriesꢀ8-10).ꢀInꢀcontrast,ꢀhigherꢀactivitiesꢀhaveꢀbeenꢀobtainedꢀ
forꢀ moreꢀ stericallyꢀ demandingꢀ PAꢀ ligands,ꢀ ie.ꢀ tBuPhPOHꢀ andꢀ
(3,5-Me -C H ) POHꢀ (entriesꢀ 16ꢀ andꢀ 11,ꢀ respectively).ꢀ
Entryꢀ
Lꢀ
d(Ru-L)ꢀ(Å)ꢀ
2.3078(10)ꢀ
2.3376(9)ꢀ
2.3120(8)ꢀ
2.3009(8ꢀ
2.3130(6)ꢀ
2.3017(10)ꢀ
2.3342(8)ꢀ
2.3680(7)ꢀ
2.313(2)ꢀ
%Vbur(L)ꢀ
21.9ꢀ
24.4ꢀ
24.6ꢀ
24.6ꢀ
22.7ꢀ
22.7ꢀ
24.1ꢀ
24.4ꢀ
23.2ꢀ
25.1ꢀ
25.6ꢀ
26.8ꢀ
24.7ꢀ
27.9ꢀ
1
2
3
4
5
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Me
2
POHꢀ
Cy
2
POHꢀ
Ph
2
POHꢀ
POHꢀ
(p-F-C
6
H
4
)
2
MePhPOHꢀ
nBuPhPOHꢀ
CyPhPOHꢀ
tBuPhPOHꢀ
2
6 3 2
Importantly,ꢀ complexesꢀ bearingꢀ phosphineꢀ orꢀ phosphiteꢀ
exhibitedꢀinterestingꢀactivitiesꢀinꢀC-Hꢀactivationꢀ(entriesꢀ18-20).ꢀ
6
Inꢀ particular,ꢀ [RuCl2(η ‐p‐cymene)(PPh3)]ꢀ wasꢀ foundꢀ moreꢀ
Ph
PCH
Ph PnBuꢀ
PPh
2
PHꢀ
selectiveꢀ forꢀ mono-functionalizationꢀ ofꢀ 2-phenylpyridineꢀ 1ꢀ
(
1
1
1
1
1
0ꢀ
1ꢀ
2ꢀ
3ꢀ
4ꢀ
Ph
2
2
OHꢀ
2.3516(8)ꢀ
2.352(2)ꢀ
entryꢀ18).ꢀ
2
Inꢀ Ru-mediatedꢀ C-Hꢀ activation,ꢀ theꢀ anionicꢀ ligandsꢀ playedꢀ anꢀ
importantꢀrole,ꢀforꢀexampleꢀcarboxylate-containingꢀcomplexesꢀ
areꢀ extremelyꢀ efficientꢀ dueꢀ toꢀ chelation-assistedꢀ C−Hꢀ
3
ꢀ
2.3438(6)ꢀ
2.2642(8)ꢀ
2.142(4)ꢀ
P(OPh)
IMesꢀ
3
ꢀ
1k,4a
activations. ꢀ Surprisingly,ꢀ toꢀ theꢀ bestꢀ ofꢀ ourꢀ knowledge,ꢀ
complexesꢀbearingꢀbromideꢀandꢀiodideꢀligandsꢀhaveꢀnotꢀbeenꢀ
investigatedꢀsoꢀfar.ꢀBromideꢀandꢀiodideꢀcounterpartsꢀbearingꢀ
tBuPhPOHꢀ phosphinousꢀ acidꢀ wereꢀ preparedꢀ withꢀ goodꢀ yieldꢀ
aꢀ
ꢀ
ParametersꢀusedꢀforꢀSambVcaꢀcalculations:ꢀ3.50ꢀÅ forꢀtheꢀsphereꢀradius,ꢀexactꢀ
distancesꢀbetweenꢀtheꢀligandꢀandꢀtheꢀmetalꢀwereꢀconsidered,ꢀhydrogenꢀatomsꢀ
ꢀ
wereꢀomittedꢀandꢀbondꢀradiiꢀscaledꢀbyꢀ1.17.
wereꢀ obtained.ꢀ Well-definedꢀ complexesꢀ performedꢀ slightlyꢀ followingꢀ theꢀ sameꢀ protocolꢀ thanꢀ forꢀ chlorideꢀ analoguesꢀ (6lꢀ
betterꢀthanꢀinꢀsitu-generatedꢀcomplexesꢀꢀ(entriesꢀ14ꢀandꢀ15)ꢀ andꢀ7lꢀrespectively,ꢀSchemeꢀ2).ꢀTheꢀactivityꢀofꢀtheseꢀcatalystsꢀ
andꢀadditionꢀofꢀanꢀextraꢀquantityꢀofꢀSPOꢀreducedꢀtheꢀcatalystꢀ wasꢀ comparedꢀ inꢀ C-Hꢀ functionalizationꢀ ofꢀ 2-phenylpyridineꢀ 1ꢀ
23
6
activity. ꢀToꢀourꢀdelight,ꢀwithꢀRuCl2(η ‐p‐cymene)(tBuPhPOH)]ꢀ andꢀ asꢀ aꢀ functionꢀ ofꢀ theꢀ arylꢀ halideꢀ partnerꢀ (Tableꢀ 6).ꢀ
l,ꢀonlyꢀcompoundꢀ3ꢀwasꢀformedꢀwithꢀanꢀalmostꢀquantitativeꢀ Unexpectedly,ꢀ drasticꢀ differencesꢀ wereꢀ observedꢀ asꢀ onlyꢀ lowꢀ
5
yieldꢀ (entryꢀ 16).ꢀ Ofꢀ note,ꢀ afterꢀ onlyꢀ 2ꢀ hꢀ ofꢀ reaction,ꢀ aꢀ 1:1ꢀ yieldsꢀofꢀC-Hꢀfunctionalizationꢀandꢀwithꢀanꢀalmostꢀequimolarꢀ
mixtureꢀofꢀmono-ꢀandꢀdiarylatedꢀproductsꢀwasꢀobservedꢀwithꢀ
ꢀ
a
Tableꢀ5EvaluationꢀofꢀcatalystsꢀperformancesꢀinꢀC-Hꢀbondꢀactivationꢀ. ꢀ
Ph-Cl
Ph
Ph
Ru Catalyst (5 mol%)
N
N
N
K2CO3, NMP, 80 °C, 24 h
Ph
1
2
3
ꢀ
Yieldꢀ(%)ꢀ
Entryꢀ
Catalystꢀ
[RuCl (p-cymene)]
Additiveꢀ
2
ꢀ
3ꢀ
b
1
2
3
4
ꢀ
ꢀ
ꢀ
ꢀ
2
2
ꢀ
ꢀ
ꢀ
0ꢀ
8ꢀ
88ꢀ
2ꢀ
c
c
c
RuCl
RuCl
RuCl
2
(p-cymene)]
(p-cymene)]
(p-cymene)]
2
ꢀ
2
2
2
2
ꢀ
ꢀ
Ad
2
P(O)Hꢀ4fꢀ(5ꢀmol%)ꢀ
0ꢀ
80ꢀ
83ꢀ
0ꢀ
Ad
2
P(O)Hꢀ4fꢀ(10ꢀmol%)ꢀ
0ꢀ
5
ꢀ
[RuCl
2
2
(p-cymene)]
(p-cymene)]
2
ꢀ
ꢀ
ꢀ
0ꢀ
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
[RuCl
6
2
Ad
2
P(O)Hꢀ4fꢀ(10ꢀmol%)ꢀ
7ꢀ
3ꢀ
[RuCl
2
(η ‐p‐cymene)(Me
2
POH)]ꢀ5aꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
14ꢀ
12ꢀ
27ꢀ
19ꢀ
32ꢀ
19ꢀ
19ꢀ
22ꢀ
21ꢀ
0ꢀ
15ꢀ
11ꢀ
22ꢀ
11ꢀ
32ꢀ
19ꢀ
11ꢀ
54ꢀ
19ꢀ
89ꢀ
13ꢀ
6ꢀ
6
[RuCl
2
(η ‐p‐cymene)(Cy
2
POH)]ꢀ5b
ꢀ
6
[RuCl
2
(η ‐p‐cymene)(Ph
2
POH)]ꢀ5c
ꢀ
6
1
1
1
1
1
1
1
0ꢀ
1ꢀ
2ꢀ
3ꢀ
4ꢀ
5ꢀ
[RuCl
2
6
(η ‐p‐cymene)((p-F-C
6
H
4
)
2
POH)]ꢀ5d
POH)]ꢀ5e
(η ‐p‐cymene)(nBuPhPOH)]ꢀ5i
ꢀ
[RuCl
[RuCl
[RuCl
[RuCl
2
(η ‐p‐cymene)((3,5-Me
2
-C
6
H
3
)
2
ꢀ
6
2
ꢀ
6
2
(η ‐p‐cymene)(BnPhPOH)]ꢀ5jꢀ
6
2
(η ‐p‐cymene)(CyPhPOH)]ꢀ5k
ꢀ
[RuCl (p-cymene)]
2
2
ꢀ
CyPhP(O)Hꢀ4kꢀ(5ꢀmol%)ꢀ
6
6ꢀ
[RuCl
[RuCl
2
(η ‐p‐cymene)(tBuPhPOH)]ꢀ5l
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
d
6
1
7 ꢀ
2
(η ‐p‐cymene)(tBuPhPOH)]ꢀ5l
ꢀ
14ꢀ
58ꢀ
18ꢀ
19ꢀ
6
1
8ꢀ
9ꢀ
0ꢀ
[RuCl
2
(η ‐p‐cymene)(PPh
3
)]ꢀ
6
1
[RuCl
2
(η ‐p‐cymene)(PCy
3
)]ꢀ
5ꢀ
6
2
[RuCl
2
(η ‐p‐cymene)(P(OPh)
3
)]ꢀ
15ꢀ
a
ꢀ
Reactionꢀconditions:ꢀ2-phenylpyridineꢀ1ꢀ(142ꢀµL,ꢀ1ꢀmmol),ꢀchlorobenzeneꢀ(220ꢀµL,ꢀ2.2ꢀmmol,ꢀ2.2ꢀequiv.),ꢀK
2
CO
3
ꢀ(415ꢀmg,ꢀ3ꢀmmol,ꢀ3ꢀequiv.),ꢀ5ꢀmol%ꢀofꢀRuꢀcomplexꢀ
b
b
d
(
2.5ꢀmol%ꢀforꢀ[RuCl
2
(p-cymene)]
2
),ꢀNMPꢀ(2ꢀmL),ꢀ80ꢀ°C,ꢀ24ꢀh.ꢀ ꢀReactionꢀperformedꢀatꢀ120ꢀ°C.ꢀ ꢀReactionꢀperformedꢀatꢀ100ꢀ°C.ꢀ ꢀReactionꢀtime:ꢀ2h.ꢀꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 5 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
View Article Online
DOI: 10.1039/C5DT04683A
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
ꢀ
a
Tableꢀ7ChlorineꢀdependenceꢀinꢀC-Hꢀactivation. ꢀ
mixtureꢀofꢀmono-ꢀandꢀdiarylationꢀwereꢀobtainedꢀ(entriesꢀ2ꢀandꢀ
).ꢀ Moreover,ꢀ whereasꢀ arylꢀ bromidesꢀ areꢀ regularlyꢀ usedꢀ asꢀ
3
couplingꢀpartner, ꢀatꢀ80ꢀ°C,ꢀtheyꢀexhibitedꢀaꢀsignificantlyꢀlowerꢀ
26
Me
iPr
OH
27
activityꢀ thanꢀ theirꢀ chlorideꢀ counterpartꢀ (entriesꢀ 4-6). ꢀ Weꢀ
assumeꢀthatꢀthisꢀisꢀdueꢀtoꢀanꢀexchangeꢀofꢀhalogensꢀbetweenꢀ
theꢀ arylꢀ halideꢀ toꢀ theꢀ metalꢀ centerꢀ occurringꢀ throughꢀ theꢀ
oxidativeꢀaddition.ꢀHalideꢀeffectsꢀinꢀtransitionꢀmetalꢀcatalysisꢀ
Cl Ru
Cl
5 mol%) R2
P
R1
(
Ph
Ph
Ph-Cl, additives
N
N
N
2 3
K CO , NMP, 80 °C, 24 h
28
areꢀ oftenꢀ difficultꢀ toꢀ rationalize, ꢀ however,ꢀ weꢀ believeꢀ thatꢀ
theꢀ iodideꢀ atomsꢀ increaseꢀ theꢀ congestionꢀ aroundꢀ theꢀ metalꢀ
Ph
1
2
3
ꢀ
29ꢀ
centerꢀandꢀdecreasesꢀitsꢀreactivity.
Yieldꢀ(%)ꢀ
Fromꢀ theseꢀ results,ꢀ aꢀ halideꢀ inhibitionꢀ wasꢀ suspected;ꢀ theꢀ
chlorineꢀ dependenceꢀ wasꢀ thereforeꢀ investigatedꢀ throughꢀ theꢀ
useꢀ ofꢀ additivesꢀ (Tableꢀ 7).ꢀ Theꢀ additionꢀ ofꢀ oneꢀ equivalentꢀ ofꢀ
LiClꢀ inꢀ theꢀ reactionꢀ mixtureꢀ quenchedꢀ indeedꢀ theꢀ C-Hꢀ
activationꢀprocessꢀ(entriesꢀ1ꢀandꢀ2).ꢀAꢀsignificantꢀlossꢀofꢀactivityꢀ
wasꢀ alsoꢀ observedꢀ withꢀ 1ꢀ equiv.ꢀ ofꢀ tetrabutylammoniumꢀ
chlorideꢀ (entryꢀ 3).ꢀ Nevertheless,ꢀ additionꢀ ofꢀ aꢀ stoichiometricꢀ
amountꢀofꢀsilverꢀsaltꢀdidꢀnotꢀboostꢀtheꢀcatalyticꢀperformancesꢀ
ofꢀcomplexesꢀexhibitingꢀaꢀmoderateꢀactivityꢀsuchꢀasꢀcomplexesꢀ
Entryꢀ
Complexꢀ5ꢀ
Additivesꢀ
2
ꢀ
3ꢀ
89ꢀ
0ꢀ
1
5lꢀ(R ,R ꢀ=ꢀPh,tBu)ꢀ
2
1
2
3
4
5
6
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Noneꢀ
0ꢀ
0ꢀ
1
5lꢀ(R ,R ꢀ=ꢀPh,tBu)ꢀ
2
LiClꢀ(1ꢀequiv.)ꢀ
1
2
5lꢀ(R ,R ꢀ=ꢀPh,tBu)ꢀ
nBu
4
NClꢀ(1ꢀequiv.)ꢀ
Noneꢀ
9ꢀ
6ꢀ
1
5aꢀ(R ,R ꢀ=ꢀMe,Me)ꢀ
2
14ꢀ
14ꢀ
0ꢀ
15ꢀ
16ꢀ
0ꢀ
1
2
5aꢀ(R ,R ꢀ=ꢀMe,Me)ꢀ
4
AgBF ꢀ(5ꢀmol%)ꢀ
1
5aꢀ(R ,R ꢀ=ꢀMe,Me)ꢀ
2
AgBF
4
ꢀ(1ꢀequiv.)ꢀ
1
2
5bꢀ(R ,R ꢀ=ꢀCy,Cy)ꢀ
7ꢀ
8ꢀ
Noneꢀ
12ꢀ
9ꢀ
11ꢀ
8ꢀ
1
5bꢀ(R ,R ꢀ=ꢀCy,Cy)ꢀ
2
AgBF
4
ꢀ(5ꢀmol%)ꢀ
1
5bꢀ(R ,R ꢀ=ꢀCy,Cy)ꢀ
2
9
ꢀ
AgBF
4
ꢀ(1ꢀequiv.)ꢀ
2ꢀ
2ꢀ
a
Me
iPr
OH
ꢀ
Reactionꢀconditions:ꢀ2-phenylpyridineꢀ1ꢀ(142ꢀµL,ꢀ1ꢀmmol),ꢀchlorobenzeneꢀ(220ꢀ
µL,ꢀ2.2ꢀmmol,ꢀ2.2ꢀequiv.),ꢀK CO ꢀ(415ꢀmg,ꢀ3ꢀmmol,ꢀ3ꢀequiv.),ꢀcomplexꢀ(5ꢀmol%),ꢀ
NMPꢀ(2ꢀmL),ꢀ24ꢀh.
O
P
[
RuX2(p-cymene)]2
2
3
X
X
Ru
tBu
H
THF, 25 °C, 3 h
ꢀ
Ph
P
Ph
tBu
X = Br: 6l (81% )
X = I: 7l (91% )
5aꢀandꢀ5bꢀ(entriesꢀ5ꢀandꢀ8).ꢀHigherꢀquantitiesꢀofꢀsilverꢀsaltꢀledꢀ
toꢀtheꢀinhibitionꢀofꢀtheꢀC-Hꢀfunctionalizationꢀ(entriesꢀ6ꢀandꢀ9).ꢀ
Theseꢀresultsꢀsuggestꢀthatꢀchlorineꢀatomsꢀplayꢀaꢀkeyꢀroleꢀinꢀtheꢀ
C-Hꢀactivationꢀprocess.ꢀꢀꢀ
4
l
ꢀ
6
Schemeꢀ 2ꢀ Synthesisꢀ ofꢀ bromide-ꢀ andꢀ iodide-containingꢀ [RuX
2
(η ‐p‐cymene)(PA)]ꢀ
complexes.
ꢀ
Inꢀorderꢀtoꢀgainꢀinsightꢀintoꢀtheꢀmechanism,ꢀinꢀparticularꢀtheꢀ
roleꢀ ofꢀ theꢀ PAꢀ ligand,ꢀ andꢀ asꢀ PAsꢀ areꢀ consideredꢀ asꢀ labileꢀ
ꢀ
a
Tableꢀ6HalogenꢀeffectꢀinꢀC-Hꢀactivation. ꢀ
15d
ligandsꢀ dueꢀ toꢀ aꢀ weakꢀ M-PAꢀ bond, ꢀ weꢀ attemptedꢀ toꢀ
determineꢀifꢀtheꢀPAꢀremainsꢀinꢀtheꢀcoordinationꢀsphereꢀofꢀtheꢀ
rutheniumꢀ allꢀ alongꢀ theꢀ catalyticꢀ cycle.ꢀ Forꢀ thisꢀ purpose,ꢀ theꢀ
Me
iPr
OH
X1 Ru
X1
P
Ph
tBu
30
(5 mol%)
Ph
Ph
rutheniumꢀ cyclometallatedꢀ complexꢀ 8ꢀ wasꢀ prepared ꢀ andꢀ
testedꢀ inꢀ catalysisꢀ (Tableꢀ 8).ꢀ Asꢀ anticipated,ꢀ atꢀ 120ꢀ °C,ꢀ thisꢀ
catalystꢀ performedꢀ wellꢀ withꢀ 91%ꢀ ofꢀ diarylatedꢀ compoundꢀ 3ꢀ
isolatedꢀ (entryꢀ 1).ꢀ However,ꢀ atꢀ 80ꢀ °C,ꢀ noꢀ reactionꢀ occurred,ꢀ
evenꢀwhenꢀtheꢀligandꢀtBuPhP(O)Hꢀ4lꢀwasꢀaddedꢀ(entriesꢀ2ꢀandꢀ
Ph-X2
N
N
N
K CO , NMP, 80 °C, 24 h
2 3
Ph
1
2
3
ꢀ
3
).ꢀInꢀoneꢀhand,ꢀtheꢀadditionꢀofꢀaꢀsubstoichiometricꢀamountꢀofꢀ
1
X ꢀ(complex)ꢀ
2
Ph-X ꢀ
Yieldꢀ(%)ꢀ
Entryꢀ
silverꢀ saltꢀ suchꢀ AgBF4ꢀ andꢀ AgSbF6ꢀ allowedꢀ theꢀ formationꢀ aꢀ
smallꢀquantitiesꢀofꢀproductsꢀ2ꢀandꢀ3ꢀ(entriesꢀ4ꢀandꢀ5).ꢀOnꢀtheꢀ
otherꢀ hand,ꢀ theꢀ combinationꢀ ofꢀ theꢀ silverꢀ saltꢀ withꢀ OPSꢀ
tBuPhP(O)Hꢀ4lꢀledꢀtoꢀrestoreꢀalmostꢀcompletelyꢀtheꢀactivityꢀofꢀ
theꢀcatalyticꢀsystemꢀ(entriesꢀ6ꢀandꢀ7).ꢀꢀ
2
ꢀ
3ꢀ
89ꢀ
18ꢀ
8ꢀ
1
2
3
4
5
6
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Clꢀ(5l)ꢀ
Brꢀ(6l)ꢀ
Iꢀ(7l)ꢀ
Ph-Clꢀ
Ph-Brꢀ
Ph-Iꢀ
0ꢀ
23ꢀ
14ꢀ
6ꢀ
Clꢀ(5l)ꢀ
Clꢀ(5l)ꢀ
Brꢀ(6l)ꢀ
Ph-Brꢀ
Ph-Iꢀ
21ꢀ
5ꢀ
3ꢀ
Weꢀ wereꢀ alsoꢀ ableꢀ toꢀ prepareꢀ quantitativelyꢀ theꢀ cationicꢀ
ruthenacycleꢀ 9cꢀ bearingꢀ aꢀ phosphinousꢀ acidꢀ ligandꢀ byꢀ theꢀ
treatmentꢀ ofꢀ complexꢀ 8ꢀ withꢀ OPSꢀ 4cꢀ inꢀ presenceꢀ ofꢀ silverꢀ
tetrafluoroborateꢀinꢀstoichiometricꢀamount.ꢀUnfortunatelyꢀ 9cꢀ
wasꢀfoundꢀtoꢀexhibitꢀnoꢀactivityꢀinꢀourꢀoptimalꢀconditionsꢀ(80ꢀꢀ
Ph-Iꢀ
3ꢀ
7ꢀ
a
ꢀ
Reactionꢀconditions:ꢀ2-phenylpyridineꢀ1ꢀ(142ꢀµL,ꢀ1ꢀmmol),ꢀarylꢀhalideꢀ(2.2ꢀmmol,ꢀ
2
.2ꢀequiv.),ꢀK CO ꢀ(415ꢀmg,ꢀ3ꢀmmol,ꢀ3ꢀequiv.),ꢀcomplexꢀ(5ꢀmol%),ꢀNMPꢀ(2ꢀmL),ꢀ24ꢀh.
2
3
ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
Page 6 of 11
ARTICLEꢀ
JournalꢀNameꢀ
a
Tableꢀ8ꢀControlꢀexperiementsꢀwithꢀruthenacycleꢀ8. ꢀ
N
Ph
View Article Online
DOI: 10.1039/C5DT04683A
Me
iPr
2
Ru
Me
iPr
Cl
N
2
K CO
3
KHCO3, KCl
Ph
Ph
Ru
Ph-Cl
Cl
Cl
R1
8
(5 mol%)
P
N
R2
N
N
HO
Ph-Cl
, NMP, 24 h
Me
iPr
R1
R2
OH
Me
iPr
K
2
CO
3
Ph
5
1
2
3
R1
ꢀ
Cl Ru
P
Ru
P
Cl
R2
N
O
Yieldꢀ(%)ꢀ
A
Entryꢀ
Additivesꢀ
Tꢀ(°C)ꢀ
H
2
ꢀ
3ꢀ
91ꢀ
0ꢀ
D
1
2
3
4
5
6
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Noneꢀ
Noneꢀ
120ꢀ
80ꢀ
80ꢀ
80ꢀ
80ꢀ
80ꢀ
0ꢀ
0ꢀ
N
tBuPhP(O)Hꢀ4lꢀ(5ꢀmol%)ꢀ
AgBF ꢀ(6ꢀmol%)ꢀ
AgSbF ꢀ(6ꢀmol%)ꢀ
ꢀ(6ꢀmol%),ꢀtBuPhP(O)Hꢀ4lꢀ
5ꢀmol%)ꢀ
ꢀ(6ꢀmol%),ꢀtBuPhP(O)Hꢀ4lꢀ
5ꢀmol%)ꢀ
0ꢀ
0ꢀ
1
Me
iPr
4
5ꢀ
4ꢀ
Me
iPr
R1
R2
R1
R2
6
7ꢀ
8ꢀ
Cl
N
Ru
P
Cl
Ru
P
H
O
AgBF
4
26ꢀ
52ꢀ
OH
(
N
7
ꢀ
AgSbF
6
80ꢀ
26ꢀ
56ꢀ
(
B
C
ꢀ
a
ꢀ
Reactionꢀconditions:ꢀ2-phenylpyridineꢀ1ꢀ(142ꢀµL,ꢀ1ꢀmmol),ꢀchlorobenzeneꢀ(220ꢀ
6
µL,ꢀ2.2ꢀmmol,ꢀ2.2ꢀequiv.),ꢀK CO
2
3
ꢀ(415ꢀmg,ꢀ3ꢀmmol,ꢀ3ꢀequiv.),ꢀcomplexꢀ8ꢀ(21.3ꢀmg,ꢀ Schemeꢀ4ꢀProposedꢀmechanismꢀforꢀtheꢀC-Hꢀactivationꢀmediatedꢀbyꢀ[RuCl (η ‐p‐
2
cymene)(PA)]ꢀcomplexes.ꢀ
ꢀmol%),ꢀNMPꢀ(2ꢀmL),ꢀ24ꢀh.ꢀ
5
withꢀ reactivityꢀ ofꢀ 9cꢀ withꢀ LiCl,ꢀ weꢀ believeꢀ theꢀ chlorineꢀ
counterattacksꢀ theꢀ metallicꢀ centerꢀ andꢀ promptsꢀ toꢀ pyridine-
moietyꢀdecoordinationꢀtoꢀaffordꢀspeciesꢀD.ꢀThisꢀstepꢀmightꢀbeꢀ
atꢀtheꢀoriginꢀofꢀtheꢀobservedꢀhalidesꢀeffect;ꢀtheꢀcounterattackꢀ
isꢀ propablyꢀ lessꢀ favoredꢀ withꢀ moreꢀ bulkyꢀ halidesꢀ suchꢀ asꢀ
bromideꢀ andꢀ iodide.ꢀ Finally,ꢀ theꢀ rateꢀ determiningꢀ oxidativeꢀ
Me
iPr
Me
iPr
BF4
Ph
Ph
AgBF4, Ph2PHO 4c
Ru
P
Ru
Cl
N
N
DCM, 22 °C, 1 h
HO
9
9%
8
9c
ꢀ
4d,32
addition
transferꢀ process ꢀ andꢀ theꢀ reductiveꢀ eliminationꢀ giveꢀ theꢀ
ꢀ occurringꢀ possiblyꢀ throughꢀ aꢀ singleꢀ electronꢀ
Schemeꢀ3ꢀPreparationꢀofꢀtheꢀcationicꢀruthenacycleꢀ9c.ꢀ
31
couplingꢀproductꢀ2ꢀandꢀreleaseꢀtheꢀcomplexꢀ5.ꢀ
C).ꢀHowever,ꢀwhenꢀthisꢀreactionꢀwasꢀpreformedꢀinꢀpresenceꢀ
°
ofꢀ 5ꢀ mol%ꢀ ofꢀ tetrabutylamoniumꢀ chloride,ꢀ 9cꢀ displayedꢀ aꢀ
moderateꢀactivityꢀwithꢀtheꢀformationꢀofꢀ11%ꢀofꢀmonoꢀarylatedꢀ
productꢀ2ꢀandꢀ14%ꢀofꢀ3.ꢀThisꢀrepresentsꢀonlyꢀaꢀslightꢀdecreaseꢀ
Conclusionsꢀ
6
ꢀ
ofꢀperformanceꢀcomparedꢀtoꢀcatalystꢀ5cꢀ(27%ꢀofꢀ2ꢀandꢀ22%ꢀofꢀ Inꢀ summary,ꢀ aꢀ seriesꢀ ofꢀ [RuCl2(η ‐p-cymene)] complexesꢀ
,ꢀTableꢀ5,ꢀentryꢀ9).ꢀToꢀfurtherꢀinvestigateꢀthisꢀchlorineꢀeffect,ꢀ bearingꢀ phosphinousꢀ acidꢀ (PA)ꢀ ligandsꢀ hasꢀ beenꢀ
complexꢀ9cꢀwasꢀtreatedꢀwithꢀ5ꢀequiv.ꢀofꢀLiClꢀinꢀCDCl3ꢀatꢀroomꢀ straightforwardlyꢀ preparedꢀ startingꢀ fromꢀ theꢀ dimerꢀ [RuCl2(p-
3
31
temperature,ꢀandꢀrapidlyꢀtheꢀ PꢀNMRꢀspectroscopyꢀshowedꢀaꢀ cymene)]2ꢀandꢀsecondaryꢀphosphineꢀoxides.ꢀTheseꢀcomplexesꢀ
newꢀresonanceꢀatꢀ108.4ꢀppmꢀwithꢀcompleteꢀdisappearanceꢀofꢀ wereꢀ fullyꢀ characterized,ꢀ notablyꢀ byꢀ single-crystalꢀ X-rayꢀ
theꢀ signalꢀ atꢀ 114.7ꢀ ppmꢀ afterꢀ onlyꢀ oneꢀ hour.ꢀ Unfortunately,ꢀ diffractionꢀ whichꢀ allowedꢀ toꢀ calculateꢀ theꢀ percentꢀ buriedꢀ
thisꢀnewꢀcompoundꢀwasꢀfoundꢀtoꢀbeꢀunstableꢀandꢀcouldꢀnotꢀbeꢀ volumesꢀ ofꢀ PAsꢀ andꢀ otherꢀ phosphorus-basedꢀ ligands.ꢀ Thisꢀ
isolatedꢀandꢀfullyꢀcharacterized.ꢀꢀ
quantificationꢀ ofꢀ theꢀ stericꢀ parameterꢀ ledꢀ toꢀ aꢀ betterꢀ
Withꢀ theseꢀ resultsꢀ inꢀ mind,ꢀ weꢀ proposeꢀ theꢀ followingꢀ comprehensionꢀofꢀtheꢀcoordinationꢀchemistryꢀforꢀthisꢀtypeꢀofꢀ
mechanismꢀ forꢀ C-Hꢀ activation/functionalizationꢀ catalyzedꢀ byꢀ complexesꢀ andꢀ explainedꢀ theꢀ absenceꢀ ofꢀ coordinationꢀ inꢀ theꢀ
6
31
[
RuCl2(η ‐p‐cymene)(PA)]ꢀ complexesꢀ 5ꢀ (Schemeꢀ 4). ꢀ Theꢀ caseꢀ ofꢀ bulkyꢀ SPOsꢀ suchꢀ asꢀ Ad2P(O)H.ꢀ Theꢀ performancesꢀ ofꢀ
mechanismꢀinitiatesꢀbyꢀaꢀbase-promotedꢀlossꢀofꢀHClꢀtoꢀgiveꢀtheꢀ theseꢀ complexesꢀ wereꢀ evaluatedꢀ inꢀ C-Hꢀ
8eꢀrutheniumꢀκ -PO-phosphinitoꢀspeciesꢀA.ꢀAꢀtransitionꢀtoꢀaꢀ activation/functionalizationꢀ ofꢀ 2-phenylpyridine.ꢀ Atꢀ 80ꢀ °C,ꢀ anꢀ
2
1
1
κ ꢀ coordinationꢀ freesꢀ aꢀ coordinationꢀ siteꢀ forꢀ theꢀ pyridine- efficientꢀ complexꢀ bearingꢀ theꢀ bulkierꢀ PAꢀ wasꢀ identified.ꢀ Aꢀ
containingꢀsubstrate.ꢀAtꢀthisꢀstage,ꢀtheꢀCDMꢀmechanismꢀmayꢀ thoroughꢀ comparisonꢀ ofꢀ arylꢀ halidesꢀ asꢀ couplingꢀ partnerꢀ
beꢀ triggeredꢀ byꢀ theꢀ phosphinitoꢀ whichꢀ interceptsꢀ theꢀ ortho- revealedꢀaꢀsharpꢀhalideꢀeffect.ꢀFurtherꢀinvestigationsꢀallowedꢀ
protonꢀwithꢀaꢀconcomitantꢀreleaseꢀofꢀtheꢀchlorineꢀatomꢀtoꢀleadꢀ toꢀestablishꢀaꢀhalideꢀdependence:ꢀlargeꢀquantitiesꢀofꢀchlorineꢀ
toꢀtheꢀcationicꢀruthenacycleꢀC.ꢀOfꢀnote,ꢀCꢀcorrespondsꢀtoꢀtheꢀ inhibitedꢀ theꢀ C-Hꢀ activation/functionalizationꢀ butꢀ
isolatedꢀcomplexꢀ9c.ꢀAccordingꢀtoꢀourꢀobservationsꢀdealingꢀꢀ
stoichiometricꢀamountsꢀwereꢀalsoꢀnecessary.ꢀOnꢀtheꢀbasisꢀofꢀ
theseꢀ resultsꢀ andꢀ theꢀ isolationꢀ aꢀ reactionꢀ intermediate,ꢀ aꢀ
2
mechanismꢀ involvingꢀ successivelyꢀ theꢀ formationꢀ ofꢀ κ -PO-
6
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 7 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
JournalꢀNameꢀ
phosphinitoꢀ species,ꢀ aꢀ concertedꢀ metallationꢀ deprotonationꢀ
ꢀARTICLEꢀ
ꢀ
View Article Online
DOI: 10.1039/C5DT04683A
6
favoredꢀ byꢀ theꢀ phosphinito,ꢀ aꢀ chlorineꢀ counterattackꢀ andꢀ [RuCl2(η -p-cymene)(Cy2POH)]ꢀ 5b.ꢀ Accordingꢀ toꢀ theꢀ generalꢀ
singleꢀelectronꢀtransferꢀoxidativeꢀadditionꢀwasꢀproposed.ꢀSinceꢀ procedure,ꢀcomplexꢀ5bꢀwasꢀobtainedꢀafterꢀ24ꢀhꢀofꢀreactionꢀasꢀ
1
theꢀ hinderedꢀ Ad2P(O)Hꢀ doesꢀ notꢀ coordinateꢀ toꢀ theꢀ metalꢀ aꢀredꢀsolidꢀ(92ꢀmg,ꢀ89%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ
Ar
centerꢀevenꢀthoughꢀitꢀimprovesꢀtheꢀC-Hꢀactivation,ꢀweꢀbelieveꢀ 5.59ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ2H,ꢀH ),ꢀ5.56ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ2H,ꢀ
Ar
thatꢀ itꢀ participatesꢀ toꢀ theꢀ CDMꢀ asꢀ anꢀ outer-sphereꢀ base.ꢀ Anꢀ H ),ꢀ 5.13ꢀ (br.ꢀ s,ꢀ 1H,ꢀ PO-H),ꢀ 2.81ꢀ (sept,ꢀ J(H,H)ꢀ =ꢀ 6.9ꢀ Hz,ꢀ 1H,ꢀ
enantioselectiveꢀ versionꢀ ofꢀ C-Hꢀ activation/functionalizationꢀ CH(CH3)2),ꢀ2.40-1.20ꢀ(m,ꢀ22H,ꢀCH2ꢀandꢀCH),ꢀ2.10ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ
13
takingꢀadvantageꢀofꢀtheꢀP-stereogenicꢀcenterꢀofꢀPAꢀligandsꢀisꢀ 1.28ꢀ (d,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 6H,ꢀ CH(CH3)2).ꢀ Cꢀ NMRꢀ (101ꢀ MHz,ꢀ
currentlyꢀunderꢀinvestigationꢀinꢀourꢀlaboratory.ꢀꢀ
Ar
CDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ107.8ꢀ(C ),ꢀ94.1ꢀ(C ),ꢀ89.0ꢀ(C -H),ꢀ84.5ꢀ(C -
Ar
Ar
Ar
H),ꢀ 42.9ꢀ (CH,ꢀ C-P),ꢀ 30.9ꢀ (CH),ꢀ 27.8-25.8ꢀ (10ꢀ CH2),ꢀ 22.3ꢀ (CH3),ꢀ
1
3
1
1
8.3ꢀ(CH3).ꢀ P{ H}ꢀNMRꢀ(162ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ129.3ꢀ(s).ꢀ
HRMSꢀ(ESI+):ꢀ m/z:ꢀ calcdꢀ forꢀ C22H37Cl2NaOPRu:ꢀ 543.0895ꢀ
Experimentalꢀ
+
M+Na] ;ꢀfound:ꢀ543.0898.ꢀ
[
ꢀ
Allꢀreagentsꢀwereꢀobtainedꢀfromꢀcommercialꢀsourcesꢀandꢀusedꢀ
asꢀ received.ꢀ Secondaryꢀ phosphineꢀ oxidesꢀ 4cꢀ andꢀ 4e-gꢀ wereꢀ
obtainedꢀfromꢀchemicalꢀsuppliers.ꢀOtherꢀSPOsꢀwereꢀpreparedꢀ
6
RuCl2(η -p-cymene)(Ph2POH)]ꢀ 5c.ꢀ Accordingꢀ toꢀ theꢀ generalꢀ
[
procedure,ꢀ complexꢀ 5cꢀ wasꢀ obtainedꢀ asꢀ aꢀ redꢀ solidꢀ (97ꢀ mg,ꢀ
33
33
34
34
35
accordingꢀtoꢀliteratureꢀprocedures:ꢀ4b, ꢀ4d, ꢀ4h, ꢀ4i, ꢀ4j, ꢀ
4
1
6%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.75-7.65ꢀ(m,ꢀ4H,ꢀ
15a 34
ꢀandꢀ4l. ꢀTHFꢀwasꢀpurifiedꢀandꢀdriedꢀoverꢀBraunꢀsolventꢀ
9
H ),ꢀ7.55-7.40ꢀ(m,ꢀ6H,ꢀH ),ꢀ5.40ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.9ꢀHz,ꢀ2H,ꢀH ),ꢀ
k
Ar
Ar
Ar
purificationꢀ systemꢀ (MB-SPS-800).ꢀ Analyticalꢀ Thinꢀ Layerꢀ
Chromatographyꢀ (TLC)ꢀ wasꢀ carriedꢀ outꢀ onꢀ Merckꢀ silicaꢀ gel60ꢀ
F254.ꢀ Productsꢀ wereꢀ revealedꢀ byꢀ ultravioletꢀ lightꢀ (254ꢀ orꢀ 366ꢀ
nm)ꢀ andꢀ stainedꢀ withꢀ dyeingꢀ reagentsꢀ solutions.ꢀ Flashꢀ
chromatographyꢀ wasꢀ performedꢀ onꢀ Combiflash®ꢀ Companionꢀ
Ar
5
.26ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ2H,ꢀH ),ꢀ2.51ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ1H,ꢀ
CH(CH3)2),ꢀ 2.01ꢀ (s,ꢀ 3H,ꢀ C-CH3),ꢀ 0.98ꢀ (d,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 6H,ꢀ
13
Ar
CH(CH3)2).ꢀ CꢀNMRꢀ(101ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ137.5ꢀ(C -P),ꢀ
Ar
31.7ꢀ (C -H),ꢀ 131.3ꢀ (C -H),ꢀ 128.4ꢀ (C -H),ꢀ 108.8ꢀ (C ),ꢀ 96.8ꢀ
Ar
Ar
Ar
1
Ar
Ar
Ar
C ),ꢀ 89.7ꢀ (C -H),ꢀ 87.0ꢀ (C -H),ꢀ 30.4ꢀ (CH),ꢀ 21.9ꢀ (CH3),ꢀ 17.9ꢀ
1
13
31
19
(
(
orꢀwithꢀMerckꢀsilicaꢀgelꢀ60ꢀ(230-400ꢀmesh).ꢀ H,ꢀ C,ꢀ Pꢀandꢀ Fꢀ
NMRꢀspectraꢀwereꢀrecordedꢀinꢀCDCl3ꢀatꢀambientꢀtemperatureꢀ
onꢀ Brukerꢀ Avanceꢀ IIIꢀ 300ꢀ orꢀ 400ꢀ spectrometersꢀ operatingꢀ atꢀ
31
1
CH3).ꢀ P{ H}ꢀ NMRꢀ (162ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 107.0ꢀ (s).ꢀ
HRMSꢀ(ESI+):ꢀ m/z:ꢀ calcdꢀ forꢀ C22H25Cl2NaOPRu:ꢀ 530.9956ꢀ
+
M+Na] ;ꢀfound:ꢀ530.9957.ꢀ
1
13
31
19
[
ꢀ
3
wereꢀ observedꢀ withꢀ Hꢀ decoupling.ꢀ Solventꢀ residualꢀ signalsꢀ
00ꢀ andꢀ 400ꢀ MHzꢀ respectivelyꢀ forꢀ H.ꢀ C,ꢀ Pꢀ andꢀ Fꢀ nucleiꢀ
1
6
RuCl2(η -p-cymene)((p-F-C6H5)2POH)]ꢀ 5d.ꢀ Accordingꢀ toꢀ theꢀ
36
[
generalꢀ procedure,ꢀ complexꢀ 5dꢀ wasꢀ obtainedꢀ afterꢀ 6ꢀ hꢀ ofꢀ
wereꢀ usedꢀ asꢀ internalꢀ standard. ꢀ Chemicalꢀ shiftsꢀ (δ)ꢀ andꢀ
couplingꢀ constantsꢀ (J)ꢀ areꢀ givenꢀ inꢀ ppmꢀ andꢀ Hzꢀ respectively.ꢀ
HRMSꢀ wereꢀ recordedꢀ onꢀ SYNAPTꢀ G2ꢀ HDMSꢀ (Waters)ꢀ orꢀ onꢀ
QStarꢀ Eliteꢀ (Appliedꢀ Biosystemsꢀ SGIEX)ꢀ equippedꢀ withꢀ anꢀ
Atmosphericꢀ Pressureꢀ Ionizationꢀ (API)ꢀ source.ꢀ Massꢀ spectraꢀ
wereꢀ obtainedꢀ aꢀ Timeꢀ Ofꢀ Flightꢀ (TOF)ꢀ analyser.ꢀ X-rayꢀ
Diffraction:ꢀIntensityꢀdataꢀwereꢀcollectedꢀonꢀaꢀBrucker-Noniusꢀ
KappaCCDꢀdiffractometerꢀusingꢀMoKαꢀradiationꢀ(0.71073ꢀÅ)ꢀatꢀ
1
reactionꢀasꢀaꢀredꢀsolidꢀ(92ꢀmg,ꢀ84%).ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl3):ꢀ
Ar
δꢀ(ppm)ꢀ=ꢀ7.75-7.65ꢀ(m,ꢀ4H,ꢀH ),ꢀ7.20-7.10ꢀ(m,ꢀ4H,ꢀH ),ꢀ5.38ꢀ
Ar
Ar Ar
d,ꢀJ(H,H)ꢀ=ꢀ5.7ꢀHz,ꢀ2H,ꢀH ),ꢀ5.27ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ2H,ꢀH ),ꢀ
(
2
1
.54ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.00ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ
13
.01ꢀ (d,ꢀ J(H,H)ꢀ =ꢀ 6.9ꢀ Hz,ꢀ 6H,ꢀ CH(CH3)2).ꢀ Cꢀ NMRꢀ (75ꢀ MHz,ꢀ
Ar
Ar
CDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ164.1ꢀ(C-F),ꢀ134.1ꢀ(C -H),ꢀ133.2ꢀ(C -P),ꢀ115.7ꢀ
Ar
C -H),ꢀ 109.3ꢀ (C ),ꢀ 97.1ꢀ (C ),ꢀ 88.7ꢀ (C -H),ꢀ 87.1ꢀ (C -H),ꢀ 30.6ꢀ
Ar
Ar
Ar
Ar
(
(
(
2
softwareꢀ package.ꢀ Theꢀ structureꢀ wasꢀ resolvedꢀ usingꢀ theꢀ
93(2)ꢀ K.ꢀ Dataꢀ reductionꢀ wasꢀ performedꢀ usingꢀ theꢀ HKL-2000ꢀ
19
1
CH),ꢀ21.7ꢀ(CH3),ꢀ18.0ꢀ(CH3).ꢀ F{ H}ꢀNMRꢀ(377ꢀMHz,ꢀCDCl3):ꢀδꢀ
31
1
37
ppm)ꢀ=ꢀ-107.6ꢀ(s).ꢀ P{ H}ꢀNMRꢀ(121ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ
05.7ꢀ(s).ꢀHRMSꢀ(ESI-):ꢀm/z:ꢀcalcdꢀforꢀC22H22Cl2OPRu:ꢀ542.9803ꢀ
softwareꢀ SIR92 ꢀ byꢀ theꢀ directꢀ methodsꢀ andꢀ refinedꢀ usingꢀ
38
1
SHELXL-97. ꢀForꢀcompoundꢀ5d,ꢀintensityꢀdataꢀwereꢀcollectedꢀ
onꢀ anꢀ Agilentꢀ SuperNovaꢀ AtlasS2ꢀ diffractometerꢀ usingꢀ MoKαꢀ
radiationꢀ (0.71073ꢀ Å)ꢀ atꢀ 293(2)ꢀ K.ꢀ Dataꢀ reductionꢀ wasꢀ
performedꢀ usingꢀ theꢀ CrysAlisProꢀ softwareꢀ packageꢀ (versionꢀ
-
M-H] ;ꢀfound:ꢀ542.9792.ꢀ
[
ꢀ
6
RuCl2(η -p-cymene)((3,5-Me2-C6H3)2POH)]ꢀ 5e.ꢀ Accordingꢀ toꢀ
[
theꢀgeneralꢀprocedure,ꢀcomplexꢀ5eꢀwasꢀobtainedꢀasꢀaꢀredꢀsolidꢀ
1
.171.37.31).ꢀ Theꢀ structureꢀ wasꢀ resolvedꢀ usingꢀ theꢀ softwareꢀ
1
103ꢀmg,ꢀ91%).ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.30ꢀ(d,ꢀ
(
J(H,P)ꢀ=ꢀ11.4ꢀHz,ꢀ4H,ꢀH ),ꢀ7.10ꢀ(s,ꢀ2H,ꢀH ),ꢀ6.51ꢀ(br.ꢀs,ꢀ1H,ꢀPO-
SHELXS-97ꢀ byꢀ theꢀ directꢀ methodsꢀ andꢀ refinedꢀ usingꢀ SHELXL-
013-4.ꢀTheꢀCIFꢀfilesꢀofꢀcompoundsꢀ5b-d,ꢀ5h,ꢀ5i,ꢀ5kꢀandꢀ5lꢀhaveꢀ
beenꢀ depositedꢀ withꢀ CCDCꢀ numbersꢀ 1434226-1434232,ꢀ
Ar
Ar
2
Ar
H),ꢀ5.40ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ2H,ꢀH ),ꢀ5.18ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ
Ar
H,ꢀH ),ꢀ2.56ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.35ꢀ(s,ꢀ12H,ꢀ
2
C-CH3),ꢀ 2.06ꢀ (s,ꢀ 3H,ꢀ C-CH3),ꢀ 0.98ꢀ (d,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 6H,ꢀ
Ar
CH(CH3)2).ꢀ Cꢀ NMRꢀ (101ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 137.8ꢀ (C ),ꢀ
respectively.ꢀꢀ
ꢀ
Generalꢀprocedureꢀforꢀtheꢀsynthesisꢀofꢀcomplexesꢀ[RuCl2(η ‐
13
6
Ar
37.7ꢀ(C ),ꢀ137.3ꢀ(C ),ꢀ136.7ꢀ(C ),ꢀ132.82ꢀ(C -H),ꢀ132.80ꢀ(C -
Ar
Ar
Ar
Ar
1
H),ꢀ 129.1ꢀ (C -H),ꢀ 129.0ꢀ (C -H),ꢀ 107.9ꢀ (C ),ꢀ 95.3ꢀ (C ),ꢀ 90.21ꢀ
arene)(PA)]ꢀ5.ꢀInꢀaꢀSchlenkꢀflask,ꢀaꢀsolutionꢀofꢀrutheniumꢀdimerꢀꢀ
[
Ar
Ar
Ar
Ar
6
RuCl2(η -p-cymene)]2ꢀ (61.2ꢀ mg,ꢀ 0.1ꢀ mmol,ꢀ 2ꢀ equiv.ꢀ ofꢀ
Ar
C -H),ꢀ 90.16ꢀ (C -H),ꢀ 87.72ꢀ (C -H),ꢀ 88.66ꢀ (C -H),ꢀ 30.3ꢀ (CH),ꢀ
Ar
Ar
Ar
(
ruthenium)ꢀ andꢀ secondaryꢀ phosphineꢀ oxideꢀ (0.22ꢀ mmol,ꢀ 2.2ꢀ
equiv.)ꢀinꢀTHFꢀ(2ꢀmL)ꢀwasꢀstirredꢀatꢀroomꢀtemperatureꢀforꢀ3ꢀh.ꢀ
Theꢀreactionꢀmixtureꢀwasꢀhalf-concentratedꢀandꢀn-hexaneꢀ(10ꢀ
mL)ꢀwasꢀaddedꢀtoꢀinitiateꢀaꢀprecipitation.ꢀTheꢀredꢀprecipitateꢀ
wasꢀ filteredꢀ offꢀ andꢀ washedꢀ withꢀ n-hexane.ꢀ Recrystallisationꢀ
fromꢀDCM/n-hexaneꢀgaveꢀcrystalsꢀofꢀtheꢀdesiredꢀproduct.ꢀ
31
1
1.6ꢀ (CH3),ꢀ 21.4ꢀ (CH3),ꢀ 17.7ꢀ (CH3).ꢀ P{ H}ꢀ NMRꢀ (121ꢀ MHz,ꢀ
2
CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 105.7ꢀ (s).ꢀ HRMSꢀ(ESI-):ꢀ m/z:ꢀ calcdꢀ forꢀ
+
C26H32Cl2NaOPRu:ꢀ563.0618ꢀ[M-H] ;ꢀfound:ꢀ563.0620.ꢀ
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ7ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
Page 8 of 11
ARTICLEꢀ
JournalꢀNameꢀ
6
RuCl2(η -p-cymene)(MePhPOH)]ꢀ5h.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ Hz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.50-2.20ꢀ(m,ꢀ2H,ꢀCHꢀandꢀCH2)V,ꢀie1w.9Ar9tiꢀc(les,Oꢀn3liHne,ꢀ
[
procedure,ꢀ complexꢀ 5hꢀ wasꢀ obtainedꢀ asꢀ aꢀ redꢀ solidꢀ (63ꢀ mg,ꢀ C-CH3),ꢀ 1.90-1.10ꢀ (m,ꢀ 9H,ꢀ CH2),ꢀ 1.10ꢀ (d,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 3H,ꢀ
DOI: 10.1039/C5DT04683A
13
1
1%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.80-7.70ꢀ(m,ꢀ2H,ꢀ CH(CH3)2),ꢀ0.75ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2).ꢀ CꢀNMRꢀ(101ꢀ
7
H ),ꢀ 7.60-7.50ꢀ (m,ꢀ 3H,ꢀ H ),ꢀ 6.15ꢀ (br.ꢀ s,ꢀ 1H,ꢀ PO-H),ꢀ 5.24ꢀ (d,ꢀ MHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ137.5ꢀ(C -P),ꢀ129.4ꢀ(C -H),ꢀ128.4ꢀ(C -
Ar
Ar
Ar
Ar
Ar
Ar
J(H,H)ꢀ=ꢀ6.3ꢀHz,ꢀ1H,ꢀH ),ꢀ5.21ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ1H,ꢀH ),ꢀ5.08ꢀ H),ꢀ127.3ꢀ(C -H),ꢀ105.6ꢀ(C ),ꢀ94.5ꢀ(C ),ꢀ93.4ꢀ(C -H),ꢀ89.3ꢀ(C -
Ar
Ar
Ar
Ar
Ar
Ar
Ar
d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ1H,ꢀH ),ꢀ5.04ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.1ꢀHz,ꢀ1H,ꢀH ),ꢀ H),ꢀ84.3ꢀ(C -H),ꢀ82.7ꢀ(C -H),ꢀ41.2ꢀ(CH-P),ꢀ29.2ꢀ(CH),ꢀ26.0-25.0ꢀ
Ar
Ar
Ar
(
31
1
.65ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.12ꢀ(d,ꢀJ(H,P)ꢀ=ꢀ10.0ꢀ (5ꢀ CH2),ꢀ 21.9ꢀ (CH3),ꢀ 19.2ꢀ (CH3),ꢀ 17.0ꢀ (CH3).ꢀ P{ H}ꢀ NMRꢀ (162ꢀ
2
Hz,ꢀ3H,ꢀP-CH3),ꢀ1.94ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ1.13ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀ MHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ114.2ꢀ(s).ꢀHRMSꢀ(ESI+):ꢀm/z:ꢀcalcdꢀforꢀ
13
+
CH(CH3)2),ꢀ1.04ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2).ꢀ CꢀNMRꢀ(101ꢀ C22H31Cl2NaOPRu:ꢀ537.0426ꢀ[M+Na] ;ꢀfound:ꢀ537.0421.ꢀ
Ar
MHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ140.9ꢀ(C -P),ꢀ131.1ꢀ(C -H),ꢀ128.9ꢀ(C -
Ar
Ar
ꢀ
H),ꢀ128.8ꢀ(C -H),ꢀ107.6ꢀ(C ),ꢀ96.1ꢀ(C ),ꢀ91.3ꢀ(C -H),ꢀ89.3ꢀ(C - [RuCl2(η -p-cymene)(tBuPhPOH)]ꢀ5l.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ
Ar
Ar
Ar
Ar
Ar
6
Ar
H),ꢀ87.6ꢀ(C -H),ꢀ86.1ꢀ(C -H),ꢀ30.5ꢀ(CH),ꢀ22.2ꢀ(CH3),ꢀ21.9ꢀ(CH3),ꢀ procedure,ꢀ complexꢀ 5lꢀ wasꢀ obtainedꢀ asꢀ aꢀ deep-redꢀ solidꢀ (97ꢀ
Ar
3
1
1
8.7ꢀ(CH3),ꢀ18.3ꢀ(CH3).ꢀ P{ H}ꢀNMRꢀ(162ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ mg,ꢀ99%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.80-7.70ꢀ(m,ꢀ
1
1
=
4
ꢀ
Ar
Ar
ꢀ 109.5ꢀ (s).ꢀ HRMSꢀ(ESI+):ꢀ m/z:ꢀ calcdꢀ forꢀ C17H23Cl2NaOPRu:ꢀ 2H,ꢀH ),ꢀ7.55-7.45ꢀ(m,ꢀ3H,ꢀH ),ꢀ6.20ꢀ(br.ꢀs,ꢀ1H,ꢀPO-H),ꢀ5.48ꢀ(d,ꢀ
+
68.9798ꢀ[M+Na] ;ꢀfound:ꢀ468.9806.ꢀ
Ar
J(H,H)ꢀ=ꢀ5.9ꢀHz,ꢀ1H,ꢀH ),ꢀ5.39ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.3ꢀHz,ꢀ1H,ꢀH ),ꢀ5.35ꢀ
Ar
Ar
Ar
(d,ꢀJ(H,H)ꢀ=ꢀ6.3ꢀHz,ꢀ1H,ꢀH ),ꢀ5.15ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ1H,ꢀH ),ꢀ
6
RuCl2(η -p-cymene)(nBuPhPOH)]ꢀ5i.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ 2.78ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.01ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ
[
procedure,ꢀ complexꢀ 5iꢀ wasꢀ obtainedꢀ asꢀ aꢀ redꢀ solidꢀ (51ꢀ mg,ꢀ 1.21ꢀ(d,ꢀJ(H,P)ꢀ=ꢀ15.0ꢀHz,ꢀ9H,ꢀC(CH3)3),ꢀ1.18ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ
1
13
3%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.80-7.70ꢀ(m,ꢀ2H,ꢀ 3H,ꢀCH(CH3)2),ꢀ1.01ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2).ꢀ CꢀNMRꢀ
5
H ),ꢀ7.60-7.45ꢀ(m,ꢀ3H,ꢀH ),ꢀ5.26ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ1H,ꢀH ),ꢀ (101ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ137.1ꢀ(C -P),ꢀ130.4ꢀ(C -H),ꢀ130.0ꢀ
Ar
Ar
Ar
Ar
Ar
Ar
.18ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ1H,ꢀH ),ꢀ5.14ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ1H,ꢀ (C -H),ꢀ128.0ꢀ(C -H),ꢀ107.6ꢀ(C ),ꢀ94.2ꢀ(C ),ꢀ92.3ꢀ(C -H),ꢀ90.5ꢀ
Ar
Ar
Ar
Ar
Ar
5
H ),ꢀ5.05ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.8ꢀHz,ꢀ1H,ꢀH ),ꢀ2.80-2.65ꢀ(m,ꢀ1H,ꢀCH2),ꢀ (C -H),ꢀ 86.6ꢀ (C -H),ꢀ 86.1ꢀ (C -H),ꢀ 39.9ꢀ (C),ꢀ 30.4ꢀ (CH),ꢀ 26.3ꢀ
Ar
Ar
Ar
Ar
Ar
31
1
2
.61ꢀ (sept,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 1H,ꢀ CH(CH3)2),ꢀ 2.25-2.10ꢀ (m,ꢀ 1H,ꢀ (CH3),ꢀ 22.0ꢀ (CH3),ꢀ 21.7ꢀ (CH3),ꢀ 18.0ꢀ (CH3).ꢀ P{ H}ꢀ NMRꢀ (162ꢀ
CH2),ꢀ1.91ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ1.65-1.15ꢀ(m,ꢀ4H,ꢀCH2),ꢀ1.11ꢀ(d,ꢀJ(H,H)ꢀ MHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ115.1ꢀ(s).ꢀHRMSꢀ(ESI+):ꢀm/z:ꢀcalcdꢀforꢀ
+
ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2),ꢀ0.97ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2),ꢀ C20H29Cl2NaOPRu:ꢀ511.0268ꢀ[M+Na] ;ꢀfound:ꢀ511.0272.ꢀ
=
13
0 ꢀ
CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 138.5ꢀ (C -P),ꢀ 130.8ꢀ (C -H),ꢀ 129.2ꢀ (C -H),ꢀ [RuBr2(η -p-cymene)(tBuPhPOH)]ꢀ6l.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ
.97ꢀ (t,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 3H,ꢀ CH2-CH3).ꢀ Cꢀ NMRꢀ (101ꢀ MHz,ꢀ
Ar
Ar
Ar
6
Ar
28.9ꢀ(C -H),ꢀ107.4ꢀ(C ),ꢀ95.7ꢀ(C ),ꢀ92.2ꢀ(C -H),ꢀ88.8ꢀ(C -H),ꢀ procedureꢀusingꢀdimerꢀ[RuBr2(η -p-cymene)]2,ꢀcomplexꢀ6lꢀwasꢀ
Ar
Ar
Ar
Ar
6
1
8
Ar
Ar
7.0ꢀ(C -H),ꢀ86.8ꢀ(C -H),ꢀ31.4ꢀ(CH2),ꢀ30.4ꢀ(CH),ꢀ24.6ꢀ(CH2),ꢀ24.0ꢀ obtainedꢀasꢀaꢀdeep-redꢀsolidꢀ(94ꢀmg,ꢀ81%).ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀ
1
31
1
CH2),ꢀ 22.2ꢀ (CH3),ꢀ 21.6ꢀ (CH3),ꢀ 18.2ꢀ (CH3),ꢀ 13.8ꢀ (CH3).ꢀ P{ H}ꢀ CDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.80-7.60ꢀ(m,ꢀ2H,ꢀH ),ꢀ7.55-7.40ꢀ(m,ꢀ3H,ꢀH ),ꢀ
Ar
Ar
(
NMRꢀ(162ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ113.1ꢀ(s).ꢀHRMSꢀ(ESI+):ꢀm/z:ꢀ 5.55ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.1ꢀHz,ꢀ1H,ꢀH ),ꢀ5.52ꢀ(br.ꢀs,ꢀ1H,ꢀPO-H),ꢀ5.41ꢀ(d,ꢀ
+
calcdꢀ forꢀ C20H29Cl2NaOPRu:ꢀ 511.0268ꢀ [M+Na] ;ꢀ found:ꢀ J(H,H)ꢀ=ꢀ6.1ꢀHz,ꢀ1H,ꢀH ),ꢀ5.37ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.2ꢀHz,ꢀ1H,ꢀH ),ꢀ5.27ꢀ
Ar
Ar
Ar
Ar
(d,ꢀ J(H,H)ꢀ =ꢀ 6.2ꢀ Hz,ꢀ 1H,ꢀ H ),ꢀ 2.93ꢀ (sept,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 1H,ꢀ
CH(CH3)2),ꢀ 2.08ꢀ (s,ꢀ 3H,ꢀ C-CH3),ꢀ 1.23ꢀ (d,ꢀ J(H,P)ꢀ =ꢀ 15.0ꢀ Hz,ꢀ 9H,ꢀ
5
ꢀ
11.0270.ꢀ
6
RuCl2(η -p-cymene)(BnPhPOH)]ꢀ5j.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ C(CH3)3),ꢀ1.20ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2),ꢀ1.04ꢀ(d,ꢀJ(H,H)ꢀ
[
procedure,ꢀ complexꢀ 5jꢀ wasꢀ obtainedꢀ asꢀ aꢀ deep-redꢀ solidꢀ (92ꢀ =ꢀ7.0ꢀHz,ꢀ3H,ꢀCH(CH3)2).ꢀ CꢀNMRꢀ(75ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ
1
mg,ꢀ88%).ꢀ HꢀNMRꢀ(300ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.70-7.60ꢀ(m,ꢀ 137.6ꢀ(C -P),ꢀ130.3ꢀ(3ꢀC -H),ꢀ127.8ꢀ(2ꢀC -H),ꢀ109.6ꢀ(C ),ꢀ94.3ꢀ
13
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
H,ꢀH ),ꢀ7.50-7.40ꢀ(m,ꢀ3H,ꢀH ),ꢀ7.10-7.00ꢀ(m,ꢀ3H,ꢀH ),ꢀ6.85- (C ),ꢀ91.8ꢀ(C -H),ꢀ91.2ꢀ(C -H),ꢀ86.6ꢀ(C -H),ꢀ85.0ꢀ(C -H),ꢀ40.7ꢀ
2
6
Ar
Ar
.75ꢀ(m,ꢀ2H,ꢀH ),ꢀ5.30-5.15ꢀ(m,ꢀ3H,ꢀH ),ꢀ5.10ꢀ(d,ꢀ J(H,H)ꢀ=ꢀ5.9ꢀ (C),ꢀ 31.1ꢀ (CH),ꢀ 26.6ꢀ (CH3),ꢀ 22.2ꢀ (CH3),ꢀ 22.1ꢀ (CH3),ꢀ 18.7ꢀ (CH3).ꢀ
3
Ar
2
31
1
Hz,ꢀ1H,ꢀH ),ꢀ4.01ꢀ(m,ꢀ1H,ꢀCH2-P),ꢀ3.54ꢀ(d,ꢀ J(H,P)ꢀ=ꢀ15.2ꢀHz,ꢀ1H,ꢀ
3
P{ H}ꢀ NMRꢀ (121ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 113.3ꢀ (s).ꢀ
CH2-P),ꢀ2.70ꢀ(sept,ꢀ J(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ1.97ꢀ(s,ꢀ3H,ꢀ HRMSꢀ(ESI+):ꢀ m/z:ꢀ calcdꢀ forꢀ C20H29Br2NaOPRu:ꢀ 600.9246ꢀ
3
3
+
C-CH3),ꢀ1.16ꢀ(d,ꢀ J(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ3H,ꢀCH(CH3)2),ꢀ1.07ꢀ(d,ꢀ J(H,H)ꢀ [M+Na] ;ꢀfound:ꢀ600.9247.ꢀ
1
3
=
ꢀ6.9ꢀHz,ꢀ3H,ꢀCH(CH3)2).ꢀ CꢀNMRꢀ(101ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ ꢀ
Ar
36.4ꢀ (C -P),ꢀ 133.7ꢀ (C ),ꢀ 131.0ꢀ (C -H),ꢀ 130.5ꢀ (C -H),ꢀ 129.7ꢀ [RuI2(η -p-cymene)(tBuPhPOH)]ꢀ 7l.ꢀ Accordingꢀ toꢀ theꢀ generalꢀ
Ar
Ar
Ar
6
1
Ar
Ar
Ar
Ar
Ar
C -H),ꢀ128.5ꢀ(C -H),ꢀ128.0ꢀ(C -H),ꢀ126.4ꢀ(C -H),ꢀ108.7ꢀ(C ),ꢀ procedureꢀ usingꢀ dimerꢀ [RuI2(η -p-cymene)]2,ꢀ complexꢀ 7lꢀ wasꢀ
6
(
Ar
7.4ꢀ(C ),ꢀ91.3ꢀ(C -H),ꢀ88.3ꢀ(C -H),ꢀ87.5ꢀ(C -H),ꢀ87.1ꢀ(C -H),ꢀ obtainedꢀ asꢀ aꢀ deep-redꢀ solidꢀ (121ꢀ mg,ꢀ 90%).ꢀ Hꢀ NMRꢀ (300ꢀ
1
8.9ꢀ(CH2),ꢀ30.4ꢀ(CH),ꢀ22.3ꢀ(CH3),ꢀ21.7ꢀ(CH3),ꢀ18.3ꢀ(CH3).ꢀ P{ H}ꢀ MHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.70-7.60ꢀ(m,ꢀ2H,ꢀH ),ꢀ7.50-7.40ꢀ(m,ꢀ
Ar
Ar
Ar
Ar
1
9
3
31
Ar
Ar
Ar
NMRꢀ(121ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ109.3ꢀ(s).ꢀHRMSꢀ(ESI+):ꢀm/z:ꢀ 3H,ꢀH ),ꢀ5.71ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.2ꢀHz,ꢀ1H,ꢀH ),ꢀ5.54ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.1ꢀ
+
calcdꢀ forꢀ C23H27Cl2NaOPRu:ꢀ 545.0113ꢀ [M+Na] ;ꢀ found:ꢀ Hz,ꢀ1H,ꢀH ),ꢀ5.43ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.1ꢀHz,ꢀ1H,ꢀH ),ꢀ5.39ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ
Ar
Ar
Ar
6.3ꢀHz,ꢀ1H,ꢀH ),ꢀ4.72ꢀ(br.ꢀs,ꢀ1H,ꢀPO-H),ꢀ3.21ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ7.0ꢀ
Hz,ꢀ1H,ꢀCH(CH3)2),ꢀ2.22ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ1.24ꢀ(d,ꢀJ(H,P)ꢀ=ꢀ14.8ꢀHz,ꢀ
5
ꢀ
45.0101.ꢀ
6
RuCl2(η -p-cymene)(CyPhPOH)]ꢀ5k.ꢀAccordingꢀtoꢀtheꢀgeneralꢀ 9H,ꢀC(CH3)3),ꢀ 1.23ꢀ (d,ꢀJ(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 3H,ꢀ CH(CH3)2),ꢀ 1.08ꢀ (d,ꢀ
[
procedure,ꢀcomplexꢀ5kꢀwasꢀobtainedꢀasꢀaꢀredꢀsolidꢀ(100ꢀmg,ꢀ J(H,H)ꢀ =ꢀ 7.0ꢀ Hz,ꢀ 3H,ꢀ CH(CH3)2).ꢀ Cꢀ NMRꢀ (75ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ
13
1
8%). HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ7.75-7.65ꢀ(m,ꢀ2H,ꢀ (ppm)ꢀ=ꢀ138.9ꢀ(C -P),ꢀ130.6ꢀ(C -H),ꢀ130.1ꢀ(C -H),ꢀ127.5ꢀ(C -
Ar
Ar
Ar
Ar
9
H ),ꢀ7.55-7.45ꢀ(m,ꢀ3H,ꢀH ),ꢀ5.52ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.5ꢀHz,ꢀ1H,ꢀH ),ꢀ H),ꢀ112.9ꢀ(C ),ꢀ95.5ꢀ(C ),ꢀ92.8ꢀ(C -H),ꢀ89.8ꢀ(C -H),ꢀ86.3ꢀ(C -H),ꢀ
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
.48ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.5ꢀHz,ꢀ1H,ꢀH ),ꢀ5.19ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.5ꢀHz,ꢀ1H,ꢀ 84.0ꢀ (C -H),ꢀ 41.3ꢀ (C),ꢀ 32.4ꢀ (CH),ꢀ 27.2ꢀ (CH3),ꢀ 23.1ꢀ (CH3),ꢀ 22.2ꢀ
Ar
5
H ),ꢀ4.90ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.5ꢀHz,ꢀ1H,ꢀH ),ꢀ2.58ꢀ(sept,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀ (CH3),ꢀ 19.9ꢀ (CH3).ꢀ P{ H}ꢀ NMRꢀ (162ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ
Ar
Ar
31
1
8
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 9 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
JournalꢀNameꢀ
13.9ꢀ(s).ꢀHRMSꢀ(ESI+):ꢀm/z:ꢀcalcdꢀforꢀC20H29I2KOPRu:ꢀ710.8726ꢀ
ꢀARTICLEꢀ
F.ꢀGlorius,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2012,ꢀ51,ꢀ102V3ie6w-1A0rt2icl5e4O;nꢀ(lihne)ꢀ
1
+
M+K] ;ꢀfound:ꢀ710.8737.ꢀ
J.ꢀYamaguchi,ꢀA.ꢀD.ꢀYamaguchiꢀandꢀK.ꢀItami,ꢀAngew.ꢀChem.ꢀ
DOI: 10.1039/C5DT04683A
[
ꢀ
Int.ꢀ Ed.,ꢀ 2012,ꢀ 51,ꢀ 8960-9009;ꢀ (i)ꢀ K.ꢀ Hiranoꢀ andꢀ M.ꢀ Miura,ꢀ
Synlett,ꢀ2011,ꢀ294-307;ꢀ(j)ꢀJ.ꢀWencel-Delord,ꢀT.ꢀDroge,ꢀF.ꢀLiuꢀ
andꢀF.ꢀGlorius,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2011,ꢀ40,ꢀ4740-4761;ꢀ(k)ꢀL.ꢀ
Ackermann,ꢀ Chem.ꢀ Rev.,ꢀ 2011,ꢀ 111,ꢀ 1315-1345;ꢀ (l)ꢀ L.ꢀ
McMurray,ꢀF.ꢀO'HaraꢀandꢀM.ꢀJ.ꢀGaunt,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2011,ꢀ
6
Ru(η -p-cymene)(Ph2POH)(2-phenylpyridine-κ -NC)BF4]ꢀ 9c.ꢀ
2
[
Inꢀaꢀround-bottomedꢀflask,ꢀwereꢀintroducedꢀinꢀturnꢀAgBF4ꢀ(56ꢀ
mg,ꢀ 0.29ꢀ mmol),ꢀ ruthenacycleꢀ 8ꢀ (122ꢀ mg,ꢀ 0.29ꢀ mmmol),ꢀ
Ph2PHOꢀ (58ꢀ mg,ꢀ 0.29ꢀ mmol)ꢀ andꢀ 5ꢀ mLꢀ ofꢀ dryꢀ DCM.ꢀ Theꢀ
reactionꢀmixtureꢀwasꢀstirredꢀatꢀroomꢀtemperatureꢀforꢀ1hꢀandꢀ
filteredꢀonꢀCelite®.ꢀVolatilesꢀremovedꢀtoꢀaffordꢀcomplexꢀ9cꢀasꢀ
4
0,ꢀ1885-1898;ꢀ(m)ꢀR.ꢀJazzar,ꢀJ.ꢀHitce,ꢀA.ꢀRenaudat,ꢀJ.ꢀSofack-
KreutzerꢀandꢀO.ꢀBaudoin,ꢀChem.ꢀEur.ꢀJ.,ꢀ2010,ꢀ16,ꢀ2654-2672.ꢀ
(a)ꢀ N.ꢀ Dastbaravardeh,ꢀ M.ꢀ Christakakou,ꢀ M.ꢀ Haiderꢀ andꢀ M.ꢀ
Schnuerch,ꢀ Synthesis,ꢀ 2014,ꢀ 46,ꢀ 1421-1439;ꢀ (b)ꢀ R.ꢀ Giri,ꢀ S.ꢀ
Thapa,ꢀ andꢀ A.ꢀ Kafle,ꢀ Adv.ꢀ Synth.ꢀ Catal.,ꢀ 2014,ꢀ 356,ꢀ 1395-
2
1
brown-greyꢀsolidꢀ(194ꢀmg,ꢀ99%).ꢀ HꢀNMRꢀ(400ꢀMHz,ꢀCDCl3):ꢀδꢀ
Ar
ppm)ꢀ=ꢀ9.27ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ5.4ꢀHz,ꢀ1H,ꢀH ),ꢀ8.09ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ7.7ꢀ
1
411;ꢀ(c)ꢀT.ꢀW.ꢀLyonsꢀandꢀM.ꢀS.ꢀSanford,ꢀChem.ꢀRev.,ꢀ2010,ꢀ
(
Hz,ꢀ1H,ꢀH ),ꢀ7.60-7.55ꢀ(m,ꢀ2H,ꢀH ),ꢀ7.50ꢀ(td,ꢀJ(H,H)ꢀ=ꢀ7.7ꢀandꢀ
Ar
Ar
110,ꢀ 1147-1169;ꢀ (d)ꢀ C.-L.ꢀ Sun,ꢀ B.-J.ꢀ Liꢀ andꢀ Z.-J.ꢀ Shi,ꢀ Chem.ꢀ
Commun.,ꢀ2010,ꢀ46,ꢀ677-685;ꢀ(e)ꢀXꢀChen,ꢀK.ꢀM.ꢀEngle,ꢀD.ꢀH.ꢀ
WangꢀandꢀJ.ꢀQ.ꢀYu,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2009,ꢀ48,ꢀ5094-
Ar
.1ꢀHz,ꢀ1H,ꢀH ),ꢀ7.36-7.29ꢀ(m,ꢀ3H,ꢀH ),ꢀ7.26-7.20ꢀ(m,ꢀ3H,ꢀH ),ꢀ
Ar
Ar
1
7
Ar
.16ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ8.2ꢀHz,ꢀ1H,ꢀH ),ꢀ7.06ꢀ(t,ꢀJ(H,H)ꢀ=ꢀ7.7ꢀHz,ꢀ1H,ꢀ
5
115.ꢀ
Ar
Ar
H ),ꢀ7.03-6.99ꢀ(m,ꢀ1H,ꢀH ),ꢀ6.78ꢀ(dt,ꢀJ(H,H)ꢀ=ꢀ8.0ꢀandꢀ2.6ꢀHz,ꢀ
3
4
(a)ꢀ F.ꢀ Hu,ꢀ Y.ꢀ Xia,ꢀ C.ꢀ Ma,ꢀ Y.ꢀ Zhangꢀ andꢀ J.ꢀ Wang,ꢀ Chem.ꢀ
Commun.,ꢀ2015,ꢀ51,ꢀ7986-7995;ꢀ(b)ꢀG.ꢀSong,ꢀF.ꢀWangꢀandꢀX.ꢀ
Li,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2012,ꢀ41,ꢀ3651-3678;ꢀ(c)ꢀD.ꢀA.ꢀColby,ꢀR.ꢀG.ꢀ
BergmanꢀandꢀJ.ꢀA.ꢀEllman,ꢀChem.ꢀRev.,ꢀ2010,ꢀ110,ꢀ624-655.ꢀꢀ
(a)ꢀL.ꢀAckermann,ꢀAcc.ꢀChem.ꢀRes.,ꢀ2014,ꢀ47,ꢀ281-295;ꢀ(b)ꢀV.ꢀ
S.ꢀ Thirunavukkarasu,ꢀ S.ꢀ I.ꢀ Kozhushkovꢀ andꢀ L.ꢀ Ackermann,ꢀ
Chem.ꢀCommun.,ꢀ2014,ꢀ50,ꢀ29-39;ꢀ(c)ꢀS.ꢀI.ꢀKozhushkov,ꢀandꢀL.ꢀ
Ackermann,ꢀChem.ꢀSci.,ꢀ2013,ꢀ4,ꢀ886-896;ꢀ(d)ꢀP.ꢀB.ꢀArockiam,ꢀ
C.ꢀ Bruneauꢀ andꢀ P.ꢀ H.Dixneuf,ꢀ Pierreꢀ H.,ꢀ Chem.ꢀ Rev.,ꢀ 2012,ꢀ
112,ꢀ5879-5918.ꢀ
(a)ꢀX.-h.ꢀCai,ꢀandꢀB.ꢀXie,ꢀSynthesis,ꢀ2015,ꢀ47,ꢀ737-759;ꢀ(b)ꢀO.ꢀ
Daugulis,ꢀH.-Q.ꢀDoꢀandꢀD.ꢀShabashov,ꢀAcc.ꢀChem.ꢀRes.,ꢀ2009,ꢀ
42,ꢀ1074-1086.ꢀ
U.ꢀFeklꢀandꢀK.ꢀI.ꢀGoldberg,ꢀAdv.ꢀInorg.ꢀChem.,ꢀ2003,ꢀ54,ꢀ259-
320.ꢀ
Ar
H,ꢀH ),ꢀ6.50ꢀ(dd,ꢀJ(H,H)ꢀ=ꢀ8.4ꢀandꢀ1.2ꢀHz,ꢀ1H,ꢀH ),ꢀ6.47ꢀ(dd,ꢀ
Ar
2
J(H,H)ꢀ=ꢀ8.2ꢀandꢀ1.0ꢀHz,ꢀ1H,ꢀH ),ꢀ6.40ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.4ꢀHz,ꢀ1H,ꢀ
Ar
Ar
H ),ꢀ6.05ꢀ(dd,ꢀJ(H,H)ꢀ=ꢀ6.4ꢀandꢀ1.4ꢀHz,ꢀ1H,ꢀH ),ꢀ5.86ꢀ(dd,ꢀJ(H,H)ꢀ
Ar
Ar Ar
ꢀ6.1ꢀandꢀ1.2ꢀHz,ꢀ1H,ꢀH ),ꢀ5.33ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.0ꢀHz,ꢀ1H,ꢀH ),ꢀ2.24ꢀ
=
(
(
sept,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ1H,ꢀCH(CH3)2),ꢀ1.88ꢀ(s,ꢀ3H,ꢀC-CH3),ꢀ0.80ꢀ
d,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ3H,ꢀCH(CH3)2),ꢀ0.72ꢀ(d,ꢀJ(H,H)ꢀ=ꢀ6.9ꢀHz,ꢀ3H,ꢀ
13
Ar
CH(CH3)2).ꢀ Cꢀ NMRꢀ (101ꢀ MHz,ꢀ CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ 171.5ꢀ (C ),ꢀ
1
Ar
71.3ꢀ (C ),ꢀ 165.0ꢀ (C ),ꢀ 156.49ꢀ (C -H),ꢀ 156.47ꢀ (C -H),ꢀ 144.9ꢀ
Ar
Ar
Ar
5
Ar
C ),ꢀ141.54ꢀ(C -H),ꢀ141.51ꢀ(C -H),ꢀ137.0ꢀ(C -H),ꢀ136.6ꢀ(C ),ꢀ
Ar
Ar
Ar
Ar
(
Ar
36.0ꢀ(C ),ꢀ132.5ꢀ(C ),ꢀ134.7ꢀ(C ),ꢀ130.3ꢀ(C -H),ꢀ130.2ꢀ(C -H),ꢀ
Ar
Ar
Ar
Ar
1
1
1
Ar
Ar
Ar
Ar
30.1ꢀ (C -H),ꢀ 130.0ꢀ (C -H),ꢀ 129.37ꢀ (C -H),ꢀ 129.35ꢀ (C -H),ꢀ
6
7
Ar
29.2ꢀ(C -H),ꢀ129.1ꢀ(C -H),ꢀ129.0ꢀ(C -H),ꢀ127.8ꢀ(C -H),ꢀ127.7ꢀ
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
(a)ꢀS.ꢀA.ꢀJohnson,ꢀDaltonꢀTrans.,ꢀ2015,ꢀ44,ꢀ10905-10913ꢀandꢀ
referencesꢀ therein;ꢀ (b)ꢀ N.ꢀ Yoshikai,ꢀ Chem.ꢀ Rec.,ꢀ 2011,ꢀ 11,ꢀ
42-251.ꢀ
K.ꢀ Gaoꢀ andꢀ N.ꢀ Yoshikai,ꢀ Acc.ꢀ Chem.ꢀ Res.,ꢀ 2014,ꢀ 47,ꢀ 1208-
219.ꢀ
(
C -H),ꢀ127.5ꢀ(C -H),ꢀ127.3ꢀ(C -H),ꢀ125.0ꢀ(C -H),ꢀ123.1ꢀ(C -H),ꢀ
Ar
Ar
Ar
Ar
Ar
22.5ꢀ(C -H),ꢀ119.3ꢀ(C -H),ꢀ113.5ꢀ(C ),ꢀ113.4ꢀ(C ),ꢀ108.5ꢀ(C ),ꢀ
1
9
2
Ar
Ar
Ar
Ar
6.61ꢀ (C -H),ꢀ 96.59ꢀ (C -H),ꢀ 96.56ꢀ (C -H),ꢀ 96.4ꢀ (C -H),ꢀ 85.3ꢀ
8
9
1
Ar
31
1
1
(
C -H),ꢀ 31.0ꢀ (CH),ꢀ 22.2ꢀ (CH3),ꢀ 22.2ꢀ (CH3),ꢀ 18.8ꢀ (CH3).ꢀ P{ H}ꢀ
19
P.ꢀL.ꢀArnold,ꢀM.ꢀW.ꢀMcMullon,ꢀJ.ꢀRiebꢀandꢀF.ꢀE.ꢀKühn,ꢀAngew.ꢀ
Chem.ꢀInt.ꢀEd.,ꢀ2015,ꢀ54,ꢀ82-100.ꢀ
NMRꢀ(162ꢀMHz,ꢀCDCl3):ꢀδꢀ(ppm)ꢀ=ꢀ114.7ꢀ(s).ꢀ FꢀNMRꢀ(376ꢀMHz,ꢀ
CDCl3):ꢀ δꢀ (ppm)ꢀ =ꢀ -150.5ꢀ (s).ꢀ HRMSꢀ(ESI+):ꢀ m/z:ꢀ calcdꢀ forꢀ
+
C33H33NOPRu:ꢀ592.1347ꢀ[M-BF4] ;ꢀfound:ꢀ592.1345.ꢀ
0 Forꢀaꢀreview,ꢀsee:ꢀ(a)ꢀM.ꢀCatellani,ꢀE.ꢀMottiꢀandꢀN.ꢀDella,ꢀAcc.ꢀ
Chem.ꢀ Res.,ꢀ 2008,ꢀ 41,ꢀ 1512-1522;ꢀ Forꢀ earlyꢀ discoveryꢀ andꢀ
significantꢀdevelopmentꢀofꢀCatellaniꢀreaction:ꢀ(b)ꢀM.ꢀCatellaniꢀ
andꢀG.ꢀP.ꢀChiusoli,ꢀJ.ꢀOrganomet.ꢀChem.,ꢀ1982,ꢀ239,ꢀC35-C37;ꢀ
(c)ꢀ M.ꢀ Catellaniꢀ andꢀ M.ꢀ C.ꢀ Fagnola,ꢀ Angew.ꢀ Chem.,ꢀ Int.ꢀ Ed.ꢀ
Engl.,ꢀ1994,ꢀ33,ꢀ2421-2422;ꢀ(d)ꢀM.ꢀCatellani,ꢀF.ꢀFrignaniꢀandꢀ
A.ꢀRangnoni,ꢀAngew.ꢀChem.,ꢀInt.ꢀEd.ꢀEngl.,ꢀ1997,ꢀ36,ꢀ119-122;ꢀ
(e)ꢀM.ꢀLautensꢀandꢀS.ꢀPiguel,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2000,ꢀ39,ꢀ
Acknowledgementsꢀ
ThisꢀworkꢀwasꢀsupportedꢀbyꢀtheꢀMinistèreꢀdeꢀl’enseignementꢀ
supérieurꢀetꢀdeꢀlaꢀrechercheꢀ(L.G.ꢀPh.D.ꢀgrant),ꢀtheꢀCNRS,ꢀAMU,ꢀ
andꢀ Centraleꢀ Marseille.ꢀ Dr.ꢀ Valérieꢀ Monnierꢀ andꢀ Christopheꢀ
Chendoꢀ (Spectropole,ꢀ Fédérationꢀ desꢀ Sciencesꢀ Chimiquesꢀ deꢀ
Marseille)ꢀ areꢀ gratefullyꢀ acknowledgedꢀ forꢀ MSꢀ analysesꢀ Weꢀ
thankꢀ Matthieuꢀ Ortegaꢀ forꢀ theꢀ preparationꢀ ofꢀ SPOs,ꢀ Dr.ꢀ
AlphonseꢀTenagliaꢀforꢀfruitfulꢀdiscussionsꢀandꢀDr.ꢀJulieꢀBroggiꢀ
forꢀusefulꢀcommentsꢀonꢀtheꢀmanuscript.ꢀWeꢀareꢀindebtedꢀtoꢀ
bothꢀrefereesꢀforꢀrelevantꢀcommentsꢀandꢀsuggestions.ꢀꢀ
1
045-1046ꢀ;ꢀ (f)ꢀ F.ꢀ Faccini,ꢀ E.ꢀ Mottiꢀ andꢀ M.ꢀ Catellani,ꢀ J.ꢀ Am.ꢀ
Chem.ꢀSoc.,ꢀ2004,ꢀ126,ꢀ78-79;ꢀ(g)ꢀC.ꢀBressy,ꢀD.ꢀAlbericoꢀandꢀ
M.ꢀLautens,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2005,ꢀ127,ꢀ13148-13145;ꢀ(h)ꢀ
B.ꢀMariampillai,ꢀJ.ꢀAlliot,ꢀM.ꢀLiꢀandꢀM.ꢀLautens,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.ꢀ2007,ꢀ129,ꢀ15372-15379;ꢀ(i)ꢀA.ꢀMartins,ꢀB.ꢀMariampillaiꢀ
andꢀ M.ꢀ Lautens,ꢀ Top.ꢀ Curr.ꢀ Chem.ꢀ 2009,ꢀ 292,ꢀ 1-33;ꢀ (j)ꢀ N.ꢀ
Della,ꢀC.ꢀG.ꢀMaestriꢀandꢀM.ꢀCatellani,ꢀChem.–Eur.ꢀJ.,ꢀ2009,ꢀ15,ꢀ
7850-7853;ꢀ(k)ꢀP.-X.ꢀShen,ꢀX.-C.ꢀWang,ꢀP.ꢀWang,ꢀR.-Y.ꢀZhuꢀandꢀ
J.-Q.ꢀYu,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2015,ꢀ137,ꢀ11574-11577.ꢀ
1
1
1 (a)ꢀ V.ꢀ I.ꢀ Sokolov,ꢀ L.ꢀ L.ꢀ Troitskayaꢀ andꢀ O.ꢀ A.ꢀ Reutov,ꢀ J.ꢀ
Organomet.ꢀChem.,ꢀ1979,ꢀ182,ꢀ537-546;ꢀ(b)ꢀD.ꢀL.ꢀDavies,ꢀS.ꢀ
M.ꢀA.ꢀDonaldꢀandꢀS.ꢀA.ꢀMacgregor,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2005,ꢀ
Notesꢀandꢀreferencesꢀ
1
27,ꢀ13754-13755;ꢀ(c)ꢀW.ꢀJ.ꢀTennꢀIII,ꢀK.ꢀJ.ꢀH.ꢀYoung,ꢀG.ꢀBhalla,ꢀ
1
Forꢀ selectedꢀ recentꢀ reviewsꢀ onꢀ C-Hꢀ activation,ꢀ see:ꢀ (a)ꢀ Z.ꢀ
Chen,ꢀ B.ꢀ Wang,ꢀ J.ꢀ Zhang,ꢀ W.ꢀ Yu,ꢀ Z.ꢀ Liuꢀ andꢀ Y.ꢀ Zhang,ꢀ Org.ꢀ
Chem.ꢀFront.,ꢀ2015,ꢀ2,ꢀ1107-1295;ꢀ(b)ꢀG.ꢀQiuꢀandꢀJ.ꢀWu,ꢀOrg.ꢀ
Chem.ꢀ Front.,ꢀ 2015,ꢀ 2,ꢀ 169-178;ꢀ (c)ꢀ L.ꢀ Yangꢀ andꢀ H.ꢀ Huang,ꢀ
Chem.ꢀRev.,ꢀ2015,ꢀ115,ꢀ3468-3417;ꢀ(d)ꢀB.ꢀLiu,ꢀF.ꢀHuꢀandꢀB.-F.ꢀ
Shi,ꢀ Daltonꢀ Trans.,ꢀ 2015,ꢀ 5,ꢀ 1883-1881;ꢀ (e)ꢀ B.ꢀ Liꢀ andꢀ P.ꢀ H.ꢀ
Dixneuf,ꢀ Chem.ꢀ Soc.ꢀ Rev.,ꢀ 2013,ꢀ 42,ꢀ 5744-5767;ꢀ (f)ꢀ J.ꢀ J.ꢀ
Mousseauꢀ andꢀ A.ꢀ B.ꢀ Charette,ꢀ Acc.ꢀ Chem.ꢀ Res.,ꢀ 2013,ꢀ 46,ꢀ
J.ꢀOxgaard,ꢀW.ꢀA.ꢀGoddardꢀIIIꢀandꢀR.ꢀA.ꢀPeriana,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ 2005,ꢀ 127,ꢀ 14172-14189;ꢀ (d)ꢀ Y.ꢀ Feng,ꢀ M.ꢀ Lail,ꢀ K.ꢀ A.ꢀ
Barakat,ꢀT.ꢀR.ꢀCundari,ꢀT.ꢀB.ꢀGunnoeꢀandꢀJ.ꢀL.ꢀPetersen,ꢀJ.ꢀAm.ꢀ
Chem.ꢀSoc.,ꢀ2005,ꢀ127,ꢀ14174-14175.ꢀꢀꢀ
2 (a)ꢀD.ꢀGarcia-Cuadrado,ꢀA.ꢀA.ꢀC.ꢀBraga,ꢀF.ꢀMaserasꢀandꢀA.ꢀM.ꢀ
Echavarren,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2006,ꢀ128,ꢀ1066-1067;ꢀ(b)ꢀD.ꢀ
García-Cuadrado,ꢀP.ꢀdeꢀMendoza,ꢀA.ꢀA.ꢀC.ꢀBraga,ꢀF.ꢀMaserasꢀ
andꢀA.ꢀM.ꢀEchavarren,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2007,ꢀ129,ꢀ6880-
4
12-424;ꢀ(g)ꢀN.ꢀKuhl,ꢀM.ꢀN.ꢀHopkinson,ꢀJ.ꢀWencel-Delordꢀandꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ9ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
Page 10 of 11
ARTICLEꢀ
JournalꢀNameꢀ
6
1
886;ꢀ(c)ꢀM.ꢀLafranceꢀandꢀK.ꢀFagnou,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2006,ꢀ 19 S.ꢀM.ꢀM.ꢀKnapp,ꢀT.ꢀJ.ꢀSherbow,ꢀR.ꢀB.ꢀYelle,ꢀJ.ꢀJ.ꢀJuVileiwetAtreticꢀlaenOdnꢀliDne.ꢀ
28,ꢀ 16496-16497;ꢀ (d)ꢀ S.ꢀ I.ꢀ Gorelsky,ꢀ D.ꢀ Lapointeꢀ andꢀ K.ꢀ R.ꢀTyler,ꢀOrganometallics,ꢀ2013,ꢀ32,ꢀ3744-3752.ꢀ
Fagnou,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2008,ꢀ130,ꢀ10848-10849;ꢀ(e)ꢀꢀK.ꢀ 20 E.ꢀY.ꢀY.ꢀChan,ꢀQ.-F.ꢀZhang,ꢀY.-K.ꢀSau,ꢀS.ꢀM.ꢀF.ꢀLo,ꢀH.ꢀH.ꢀY.ꢀSung,ꢀ
DOI: 10.1039/C5DT04683A
M.ꢀ Engle,ꢀ P.ꢀ S.ꢀ Thuy-Boun,ꢀ M.ꢀ Dangꢀ andꢀ J.-Q.ꢀ Yu,ꢀ J.ꢀ Am.ꢀ
Chem.ꢀSoc.,ꢀ2011,ꢀ133,ꢀ18183-18193.ꢀꢀ
I.ꢀD.ꢀWilliams,ꢀR.ꢀK.ꢀHaynesꢀandꢀW.-H.ꢀLeung,ꢀInorg.ꢀChem.,ꢀ
2004,ꢀ43,ꢀ4921-4926.ꢀ
1
1
3 (a)ꢀL.ꢀN.ꢀLewisꢀandꢀJ.ꢀF.ꢀSmith,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ1986,ꢀ108,ꢀ 21 E.ꢀ Tomás-Mendivil,ꢀ L.ꢀ Menéndez-Rodriguez,ꢀ J.ꢀ Francos,ꢀ P.ꢀ
728–2735;ꢀ(b)ꢀE.ꢀJ.ꢀMoore,ꢀW.ꢀR.ꢀPretzer,ꢀT.ꢀJ.ꢀO'Connell,ꢀJ.ꢀ CrochetꢀandꢀV.ꢀCadierno,ꢀRSCꢀAdv.,ꢀ2014,ꢀ4,ꢀ63466-63474.ꢀ
Harris,ꢀL.ꢀLaBounty,ꢀL.ꢀChouꢀandꢀS.ꢀS.ꢀGrimmer,ꢀJ.ꢀAm.ꢀChem.ꢀ 22 Duringꢀ theꢀ redactionꢀ ofꢀ theꢀ manuscript,ꢀ theꢀ synthesisꢀ ofꢀ
2
6-
Soc.,ꢀ 1992,ꢀ 114,ꢀ 5888–5890;ꢀ (c)ꢀ S.ꢀ Murai,ꢀ F.ꢀ Kakiuchi,ꢀ S.ꢀ
Sekine,ꢀY.ꢀTanaka,ꢀA.ꢀKamatani,ꢀM.ꢀSonodaꢀandꢀN.ꢀChatani,ꢀ
Nature,ꢀ1993,ꢀ366,ꢀ529-531;ꢀ(d)ꢀF.ꢀKakiuchi,ꢀS.ꢀKan,ꢀK.ꢀIgi,ꢀN.ꢀ
Chatani,ꢀandꢀS.ꢀMurai,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2003,ꢀ125,ꢀ1698-
2
otherꢀ [RuCl (η arene)(PA)]ꢀ complexes,ꢀ includingꢀ 5cꢀ wasꢀ
reported,ꢀ see:ꢀ E.ꢀ Tomás-Mendivil,ꢀ V.ꢀ Cadierno,ꢀ M.ꢀ I.ꢀ
Menéndezꢀ andꢀ R.ꢀ López,ꢀ Chem.ꢀ Eur.ꢀ J.,ꢀ 2015,ꢀ 21,ꢀ 16874-
16886.ꢀꢀ
1
699.ꢀ
23 Forꢀdetails,ꢀseeꢀsupportingꢀinformation.ꢀꢀ
4 Forꢀselectedꢀreferences,ꢀsee:ꢀ(a)ꢀS.ꢀOi,ꢀY.ꢀFukita,ꢀN.ꢀWatanuli,ꢀ 24 H.ꢀClavierꢀandꢀS.ꢀP.ꢀNolan,ꢀChem.ꢀCommun.,ꢀ2010,ꢀ49,ꢀ841-
S.ꢀMiyanoꢀandꢀY.ꢀInoueꢀOrg.ꢀLett.,ꢀ2001,ꢀ3,ꢀ2579-2581;ꢀ(b)ꢀI.ꢀ 861.ꢀ
Özdemir,ꢀS.ꢀDemir,ꢀB.ꢀÇetinkaya,ꢀC.ꢀGourlauoen,ꢀF.ꢀMaseras,ꢀ 25 (a)ꢀA.ꢀC.ꢀHillier,ꢀW.ꢀJ.ꢀSommer,ꢀB.ꢀS.ꢀYong,ꢀJ.ꢀL.ꢀPetersen,ꢀL.ꢀ
C.ꢀBruneauꢀandꢀP.ꢀH.ꢀDixneuf,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2008,ꢀ130,ꢀ
156-1157;ꢀ (c)ꢀ P.ꢀ B.ꢀ Arochiam,ꢀ C.ꢀ Fischmeister,ꢀ C.ꢀ Bruneauꢀ
andꢀ P.ꢀ H.ꢀ Dixneuf,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ 2010,ꢀ 49,ꢀ 6629-
632;ꢀ(d)ꢀE.ꢀFerrerꢀFlegeau,ꢀC.ꢀBruneau,ꢀP.ꢀH.ꢀDixneufꢀandꢀA.ꢀ
Jutand,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2011,ꢀ133,ꢀ10161-10170;ꢀ(e)ꢀS.ꢀR.ꢀ
Cavalloꢀ andꢀ S.ꢀ P.ꢀ Nolan,ꢀ Organometallics,ꢀ 2003,ꢀ 22,ꢀ 4322-
4326;ꢀ (b)ꢀ A.ꢀ Poater,ꢀ B.ꢀ Cosenza,ꢀ A.ꢀ Correa,ꢀ S.ꢀ Giudice,ꢀ F.ꢀ
Ragone,ꢀV.ꢀScaranoꢀandꢀL.ꢀCavallo,ꢀEur.ꢀJ.ꢀInorg.ꢀChem.ꢀ2009,ꢀ
1
6
1759-1766;ꢀ
https://www.molnac.unisa.it/OMtools/sambvca.phpꢀ
(c)ꢀ
Chipudi,ꢀI.ꢀKhanꢀandꢀH.ꢀW.ꢀLam,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2012,ꢀ 26 Forꢀ selectedꢀ examples,ꢀ see:ꢀ (a)ꢀ N.ꢀ Y.ꢀ P.ꢀ Kumar,ꢀ R.ꢀ
5
1,ꢀ12115-12119;ꢀ(f)ꢀJ.ꢀZhangꢀandꢀT.-P.ꢀLoh,ꢀChem.ꢀCommun.,ꢀ
012,ꢀ48,ꢀ11232-11234;ꢀ(g)ꢀM.ꢀC.ꢀReddyꢀandꢀM.ꢀJeganmohan,ꢀ
Jeyachandranꢀ andꢀ L.ꢀ Ackermann,ꢀ J.ꢀ Org.ꢀ Chem.,ꢀ 2013,ꢀ 78,ꢀ
4145-4152;ꢀ(b)ꢀM.ꢀSeki,ꢀRSCꢀAdv.,ꢀ2014,ꢀ4,ꢀ29131-29133.ꢀ
2
Chem.ꢀCommun.,ꢀ2013,ꢀ49,ꢀ481-483;ꢀ(h)ꢀR.ꢀK.ꢀChinnagolla,ꢀS.ꢀ 27 Forꢀ aꢀ rareꢀ exampleꢀ ofꢀ thoroughꢀ comparisonꢀ betweenꢀ arylꢀ
PimparkarꢀandꢀM.ꢀJeganmohan,ꢀChem.ꢀCommun.,ꢀ2013,ꢀ49,ꢀ halides,ꢀsee:ꢀreferenceꢀ16b.ꢀ
703-3705;ꢀ(i)ꢀG.ꢀRouquetꢀandꢀN.ꢀChatani,ꢀChem.ꢀSci.,ꢀ2013,ꢀ 28 K.ꢀFagnouꢀandꢀM.ꢀLautens,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2002,ꢀ41,ꢀ
,ꢀ2201-2208;ꢀ(j)ꢀP.ꢀB.ꢀArochiam,ꢀC.ꢀFischmeister,ꢀC.ꢀBruneauꢀ 26-47.ꢀ
3
4
andꢀP.ꢀH.ꢀDixneuf,ꢀGreen.ꢀChem.,ꢀ2013,ꢀ15,ꢀ67-71;ꢀ(k)ꢀD.ꢀG.ꢀ 29 TheꢀionicꢀradiiꢀofꢀClꢀandꢀIꢀareꢀ167ꢀpmꢀandꢀ207ꢀpm,ꢀandꢀtheirꢀ
Johnson,ꢀ J.ꢀ M.ꢀ Lynam,ꢀ N.ꢀ S.ꢀ Mistry,ꢀ J.ꢀ M.ꢀ Slattery,ꢀ R.ꢀ J.ꢀ
ThatcherꢀandꢀA.ꢀC.ꢀWhitwood,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2013,ꢀ135,ꢀ
2222-2234;ꢀ(l)ꢀN.ꢀHofmannꢀandꢀL.ꢀAckermann,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.ꢀ 2013,ꢀ 135,ꢀ 5877-5884;ꢀ (m)ꢀ M.ꢀ Shang,ꢀ S.-H.ꢀ Zeng,ꢀ S.-Z.ꢀ
covalentꢀ radiiꢀ areꢀ 99ꢀ pmꢀ andꢀ 133ꢀ pm,ꢀ respectively;ꢀ J.ꢀ E.ꢀ
Huheey,ꢀE.ꢀA.ꢀKeiterꢀandꢀR.ꢀL.ꢀKeiter,ꢀinꢀInorganicꢀChemistry:ꢀ
Principlesꢀ ofꢀ Structureꢀ andꢀ Reactivity,ꢀ Harperꢀ Collins:ꢀ Newꢀ
York,ꢀ1993,ꢀChapterꢀ13.ꢀ
Sun,ꢀH.-X.ꢀDaiꢀandꢀJ.-Q.ꢀYu,ꢀOrg.ꢀLett.,ꢀ2013,ꢀ15,ꢀ5286-5289;ꢀ 30 B.ꢀLi,ꢀT.ꢀRoisnel,ꢀC.ꢀDarcelꢀandꢀP.ꢀH.ꢀDixneuf,ꢀDaltonꢀTrans.,ꢀ
(
(
n)ꢀP.ꢀM.ꢀLiuꢀandꢀC.ꢀG.ꢀFrost,ꢀOrg.ꢀLett.,ꢀ2013,ꢀ15,ꢀ5862-5865;ꢀ
o)ꢀ Z.ꢀ Zhang,ꢀ H.ꢀ Jiangꢀ andꢀ Y.ꢀ Huang,ꢀ Org.ꢀ Lett.,ꢀ 2014,ꢀ 16,ꢀ 31 Duringꢀ theꢀ reviewingꢀ processꢀ ofꢀ thisꢀ manuscript,ꢀ aꢀ similarꢀ
2012,ꢀ41,ꢀ10934-10937.ꢀ
5
976-5979;ꢀ (p)ꢀ S.ꢀ Nakanowatariꢀ andꢀ L.ꢀ Ackermann,ꢀ Chem.ꢀ
Eur.ꢀJ.,ꢀ2014,ꢀ20,ꢀ5409-5413.ꢀ
mechanismꢀ wasꢀ proposedꢀ byꢀ Ackermann,ꢀ see:ꢀ D.ꢀ Zell,ꢀ S.ꢀ
Warrataz,ꢀD.ꢀGelman,ꢀS.ꢀJ.ꢀGardenꢀandꢀL.ꢀAckermann,ꢀChem.ꢀ
Eur.ꢀJ.,ꢀ2016,ꢀ22,ꢀ1248-1252.ꢀ
1
5 (a)ꢀJ.ꢀBigeault,ꢀL.ꢀGiordanoꢀandꢀG.ꢀBuono,ꢀAngew.ꢀChem.ꢀInt.ꢀ
Ed.,ꢀ2005,ꢀ44,ꢀ4753-4757;ꢀ(b)ꢀJ.ꢀBigeault,ꢀL.ꢀGiordano,ꢀI.ꢀDeꢀ 32 L.ꢀAckermann,ꢀR.ꢀVicente,ꢀH.ꢀK.ꢀPotukuchiꢀandꢀV.ꢀPirovano,ꢀ
Riggi,ꢀ Y.ꢀ Gimbertꢀ andꢀ G.ꢀ Buono,ꢀ Org.ꢀ Lett.,ꢀ 2007,ꢀ 9,ꢀ 3567- Org.ꢀLett.,ꢀ2010,ꢀ12,ꢀ5032-5035.ꢀ
570;ꢀ(c)ꢀT.ꢀAchard,ꢀL.ꢀGiordano,ꢀA.ꢀTenaglia,ꢀY.ꢀGimbertꢀꢀandꢀ 33 C.ꢀ A.ꢀ Busacca,ꢀ J.ꢀ C.ꢀ Lorenz,ꢀ N.ꢀ Grinberg,ꢀ N.ꢀ Haddad,ꢀ M.ꢀ
3
G.ꢀ Buono,ꢀ Organometallics,ꢀ 2010,ꢀ 29,ꢀ 3936-3950;ꢀ (d)ꢀ D.ꢀ
Martin,ꢀD.ꢀMoraleda,ꢀT.ꢀAchard,ꢀL.ꢀGiordanoꢀandꢀG.ꢀBuono,ꢀ
Chem.ꢀ Eur.ꢀ J.,ꢀ 2011,ꢀ 17,ꢀ 12729-12740;ꢀ (e)ꢀ T.ꢀ Achard,ꢀ A.ꢀ
Hrapchak,ꢀB.ꢀLatli,ꢀH.ꢀLee,ꢀP.ꢀSabila,ꢀA.ꢀSaha,ꢀM.ꢀSarvestani,ꢀS.ꢀ
Shen,ꢀR.ꢀvarsolona,ꢀX.ꢀWeiꢀandꢀC.ꢀH.ꢀSenannayake,ꢀOrg.ꢀLett.,ꢀ
2005,ꢀ7,ꢀ4277-4280.ꢀ
Lepronier,ꢀ Y.ꢀ Gimbert,ꢀ H.ꢀ Clavier,ꢀ L.ꢀ Giordano,ꢀ A.ꢀ Tenagliaꢀ 34 A.ꢀ Leyris,ꢀ J.ꢀ Bigeault,ꢀ D.ꢀ Nuel,ꢀ L.ꢀ Giordanoꢀ andꢀ G.ꢀ Buono,ꢀ
andꢀG.ꢀBuono,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2011,ꢀ50,ꢀ3352-3356;ꢀ TetrahedronꢀLett.,ꢀ2007,ꢀ48,ꢀ5247-5250.ꢀ
f)ꢀ H.ꢀ Clavier,ꢀ A.ꢀ Lepronier,ꢀ N.ꢀ Bengobesse-Mintsa,ꢀ D.ꢀ 35 T.ꢀL.ꢀEmmickꢀandꢀR.ꢀL.ꢀLetsinger,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ1968,ꢀ90,ꢀ
(
Gatineau,ꢀ H.ꢀ Pellissier,ꢀ L.ꢀ Giordano,ꢀ A.ꢀ Tenaglia,ꢀ G.ꢀ Buono,ꢀ 3459-3465.ꢀ
Adv.ꢀ Synth.ꢀ Catal.,ꢀ 2013,ꢀ 355,ꢀ 403-408;ꢀ (g)ꢀ F.ꢀ Schröder,ꢀ C.ꢀ 36 G.ꢀR.ꢀFulmer,ꢀA.ꢀJ.ꢀM.ꢀMiller,ꢀN.ꢀH.ꢀSherden,ꢀH.ꢀE.ꢀGottlieb,ꢀA.ꢀ
Tugny,ꢀE.ꢀSalanouve,ꢀH.ꢀClavier,ꢀL.ꢀGiordano,ꢀD.ꢀMoraleda,ꢀY.ꢀ
Gimbert,ꢀ V.ꢀ Mouriès-Mansuy,ꢀ J-P.ꢀ Goddardꢀ andꢀ L.ꢀ
Nudelman,ꢀ B.ꢀ M.ꢀ Stoltz,ꢀ J.ꢀ E.ꢀ Bercawꢀ andꢀ K.ꢀ I.ꢀ Goldberg,ꢀ
Organometallics,ꢀ2010,ꢀ29,ꢀ2176-2179.ꢀ
Fensterbank,ꢀOrganometallics,ꢀ2014,ꢀ33,ꢀ4051-4056;ꢀ(h)ꢀL.ꢀV.ꢀ 37 A.ꢀAltomare,ꢀG.ꢀCascarano,ꢀC.ꢀGiacovazzoꢀandꢀA.ꢀGuagliardi,ꢀJ.ꢀ
Graux,ꢀM.ꢀGiorgi,ꢀG.ꢀBuonoꢀandꢀH.ꢀClavier,ꢀOrganometallics,ꢀ Appl.ꢀCryst.,ꢀ1993,ꢀ26,ꢀ343-350.ꢀ
015,ꢀ 34,ꢀ 1864-1871;ꢀ (i)ꢀ P.ꢀ Nava,ꢀ H.ꢀ Clavier,ꢀ Y.ꢀ Gimbert,ꢀ L.ꢀ 38 G.ꢀM.ꢀSheldrick,ꢀActaꢀCryst.,ꢀ2008,ꢀA64,ꢀ112-122.ꢀ
Giordano,ꢀG.ꢀBuonoꢀandꢀS.ꢀHumbel,ꢀChemCatChem,ꢀ2015,ꢀ7,ꢀ
848-3854.ꢀ
2
3
1
1
6 ꢀL.ꢀAckermann,ꢀOrg.ꢀLett.,ꢀ2005,ꢀ7,ꢀ3123-3125.ꢀ
7 (a)ꢀL.ꢀAckermann,ꢀA.ꢀAlthammerꢀandꢀR.ꢀBornꢀAngew.ꢀChem.ꢀ
Int.ꢀEd.,ꢀ2006,ꢀ45,ꢀ2619-2622;ꢀ(b)ꢀL.ꢀAckermann,ꢀR.ꢀBornꢀandꢀ
P.Álvarez-Bercedoꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2007,ꢀ 46,ꢀ 6364-
6
367;ꢀ(c)ꢀL.ꢀAckermann,ꢀR.ꢀVincenteꢀandꢀA.ꢀAlthammerꢀOrg.ꢀ
Lett.,ꢀ2008,ꢀ10,ꢀ3123-3125;ꢀ(d)ꢀL.ꢀAckermannꢀandꢀM.ꢀMulzer,ꢀ
Org.ꢀLett.,ꢀ2008,ꢀ10,ꢀ5043-5045;ꢀ(e)ꢀL.ꢀAckermannꢀandꢀA.ꢀV.ꢀ
Lygin,ꢀOrg.ꢀLett.,ꢀ2011,ꢀ13,ꢀ3332-3335.ꢀ
1
8 R.ꢀKrafczyk,ꢀH.ꢀThönnessen,ꢀP.ꢀG.ꢀJonesꢀandꢀR.ꢀSchmutzler,ꢀJ.ꢀ
FluorineꢀChem.,ꢀ1997,ꢀ83,ꢀ159-166.ꢀ
1
0ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 11 of 11
Ple aDs ae lꢀ dt oo nꢀ n To rt aꢀ an d sj ua cs tt ꢀi mo na sr ginsꢀ
View Article Online
DOI: 10.1039/C5DT04683A
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
Graphicalꢀabstractꢀ
ꢀ
H
N
Me
Cl
iPr
R1
Me
iPr
Me
iPr
N
Ph
R2
Base
Ru
P
Ph-Cl
R1
R2
OH
Ru
Ru
P
Cl
Cl
R1
Cl
N
P
O
R2
HO
9
well-defined catalysts
isolated intermediate
ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ11ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ