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11. Palladium 1993
Coordination Chemistry Reviews 144 (1995)
ELSEVIER
11.
Peter
409-429
Palladium
1993
K. Byers
CONTENTS INTRODUCTION .................................................................................................... 409 11.l PALLADIUM(IV) ............................................................................................ 409 11.2 PALLADIUM(I1) ............................................................................................. 410 11.2.1 Complexes with phosphine donor ligands ................................. 410 11.2.2 Complexes with nitrogen donor ligands .................................... 417 11.2.3 Cyclometallation complexes ......................................................420 Complexes with sulfur donor ligands ....................................... 422 11.2.4 Complexes with mixed donor ligands ....................................... 423 11.2.5 11.3 PALLADIUM(I) .............................................................................................. 425 11.4 PALLADIUM(O) .............................................................................................. 426 REFERENCES .......................................................................................................... 427
INTRODUCTION
The coordination chemistry of palladium reported during the year 1993 has been reviewed. Although this account does not intend or claim to be comprehensive, examples have been selected to represent important features. Only the primary journals are covered and were searched for both palladium (and related) as a keyword and being present in the title. The review covers the chemistry of palladium in its 0 + +4 oxidation states, but does not include the catalytic activity of palladium complexes or complexes containing only Pd-C bonds. Classification of the complexes is according to the oxidation state and donor atom. For complexes containing mixed donor sets the priority ordering P>N>S applies, and neutral donors have priority over charged donor atoms; mixed donor didentate ligands are treated separately. 11.1
PALJADIUM(IV)
The new palladium(W)
complex
(1) has been prepared by oxidative
addition of
p-nitrobenzyl bromide to the corresponding parent di-organ0 species. In solution, benzyl group migration to the aromatic site slowly occurs with complete regioselectivity, and with a concomitant decrease in the palladium oxidation state [ 11. OOIO-8545/95/$09.500 1995 Elsevier Science S.A. All rights nxerved SXN OOlO-8545(95)01205-5
410
P.K. Byers/Coordin&m
Palladium(IV)
complexes
subjected to Electrospray
Chemistry Reviews 146 (1995) 409-429
containing
Mass Spectrometry.
ligands such as those displayed
in (2) have been
In the majority of cases, the intact ion was observed
as the base peak at low ion source energies. At higher source energies the palladium(IV) compounds all underwent facile reductive elimination of two methyl groups, as expected [2].
11.2
PALLADIUM(IIJ
11.2.1
Complexes withphosphine
Reaction of [PdX2(PR3)2] EBtt$Itt]
donor ligands
(X = Cl, I; PR3 = PPh3, PMePh2, PMe2Ph) with the nido-[7-
CE=Se, Te) anions has been reported [3]. In thf at ambient temperature twelve vertex [2,2-
(PR3)2-cZoso-2,1-PdEBl~l0]
(3) is obtained, whilst in refluxing toluene reaction produces only
[2-X-2-(PPh3)-cZoso-2,1-PdTeBlgHg(PPh3)]
(4). Further reaction of (4) (X = I) with HgII salts
affords [2-X-2-(PPh3)-cZoso-2,1-PdTeBt&(PPh3)]
(X = Cl, Br, CN, SCN or 02CMe) complexes
(4). The solid state structure of (3; PR3 = PMe2Ph) and (4; X = 02CMe) were determined X-ray diffraction
(H20)-2-(PPh3)-cZoso-2,l-PdTeBtoHg(PPh3)][BF4] determined
using
methods [4]. Further, (4; X = I) when treated with AgBF4 in toluene gave [2(S), whose solid state structure has been
by single crystal X-ray diffraction.
The Hz0 molecule of (5) can be replaced by a
variety of ligands to produce cationic complexes
[2-L-2-(PR3)-closo-2,1-PdTeB$-I9(PPh3)l[BF4l
(L = e.g. CO, CNBu’, NCMe, OC4H8. SC4Hg) (5). In the case of (5; L = CO) the solid state structure of the molecule has been determined by X-ray crystallography In a related report, [PdClz(PMe2Ph)2] dianions to produce the bis(phosphine)palladium
reacted with the nido-[7,8-E2BgHg]2diheteroboranes
(6) were obtained, and their solid structures subsequently
t51.
[4]. (E = As, Sb)
(6). Crystals of the complexes
determined
by X-ray diffraction
studies
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 409-429
w+
(4)
(3)
. = B-H
. =B-H E=As,Sb
PhMep P The preparation has been reported, derivatives
/‘“\
PMe ,Ph
of [Pd(p-Br)2&][NBu&
and these complexes
(6)
and [PdR2(NCMe)21 (R = p-MeCeH602CH2)
have subsequently
of general formula [PdBrR2L][NBu4]
been used to prepare
convenient procedure for the synthesis of the dinuclear methylpalladium(I1) CI)(PR3)2]
(PR3 = PEt3, PBu3, PMezPh,
complexes
PMePh2 and PPh3) (7) has appeared.
involves reaction of [PdCl&-C1)2(PR3)2]
with SnMe4 in benzene at room temperature.
(7) react with pyrazoles
of base to give the pyrazolato-bridged
in the presence
Both (7) and (8) adopt a trans-configuration
u3P\A jMe M ,/‘“\,
a series of
and [PdRzLT] (L = e.g. PR3, 4-Mepy)
[PdzMeZ(pThe method The dimers
compounds
[7].
6
R3P
1
/N-N\
Me /
‘Y PR3
PR3
(7)
(8)
[7]. A
(8).
P.K. Byers/Coordination
412
Thermolysis
Chemisrv
Reviews
of the dimer [Pd$12( ~-tBu2P(CH2)sPtBu2)2]
X = Cl) containing the P,C,P’-tridentate
protonated
with [HNMe3][BF4]
complex is readily displaced by coordinating [Pd(H20)L][BPb]
409-429
readily affords the complex (9;
ligand (L). Metathesis of this complex with MeLi or LiAELt
produces the analogous methyl and hydride complexes can be selectively
146 (1995)
solvents.
(9; X = H, Me), and complex (9; X = Me) to yield [Pd(BFd)L];
the BF4 ligand in the
The solid state structures of [PdMe(L)] and
were determined using X-ray diffraction methods [8].
Pd-P PBu t2 I
But2
x
X=Cl,H,Me (9)
Treatment with base of n-allylpalladium 2-position
complexes bearing a methoxymethoxy
has been reported to give the corresponding
contrast to the formation of 2-hydroxy-substituted
oxodimethylenemethane
group at the
complex (10) in
tt-alkyl complexes (11) via acidic hydrolysis [9].
0
(10)
(11)
A series of cyclopentadienyl
complexes
of the type [Pd(tl5-C5H5)(CH2Z)(PPh3)]
COPh, COMe, COCH2C1, CN, SMe) (12) have been prepared and characterised. all react with dry HCl to give [Pd(q%sHs)Cl(PPh3)] [PdC12(PPh3)]2
[ 101. The palladium
triflate complexes
and finally dimeric
[Pd(OTF)z(P-P)]
(P-P = dppm, dppe,
characterised
(13); the solid state structure of (13;
using X-ray diffraction methods [ 111. Cyclopentadienylpalladium(I1)
complexes have also been obtained by with [Pd2Ph2(FL-OH)2L2]
The complexes
as an intermediate,
dppp) react with Tl(CsHs) to produce the cationic complexes P-P = dppe) was determined
(Z =
direct
reaction of cyclopentadiene
(L = PPh3, PCy3). The complex
by single crystal X-ray diffraction [12].
or methylcyclopentadiene
(14; L = PPh3) was structurally
P.K. Byers/Coordination
Chemistry
I
square planar cis-alkyl(carbony1)
spectroscopy complexes
(14)
[13]. The insertion
was
(15) has been described.
prepared
((S,S)-BDPP
by halide
of CO, and was identified
of isocyanides
affords new (metallovinyl)ketenimine
transition metal complex containing a chelating
[Pd(Me)(CO)((S,S)-BDPP]][BF4]
(2S,4S)-2,4_bis(diphenylphosphino)pentane] in the presence
413
PhAPd\L
(13)
has been reported. The complex,
[PdMeCl((S,S)-BDPP)]
409-429
I
p/pd\p
PPh 3
(12)
Thejirst
146 (1995)
I
ZH 2CApd\
diphosphine
Reviews
abstraction
=
from
using high pressure
NMR
into the M-C bond of (o-allenyl)palladium(II)
When the R groups on the allenyl ligand are small, insertion compounds
rrans-[PdX[
C(CRR’)(CH=C=NR”))
(PPh3)2]
(16) 1141.
-
The complex PhCOCH2Cl palladium.
Ph3P
[Pd(CH2COPh)(Cl)(PPh3)2]
to [Pd(PPh&],
has been prepared
and X-ray analysis has revealed
X
by oxidative
addition of
the enolate to be C-bonded
to
The complex inserts a tBuNC molecule into the Pd-C bond to form trans-[Pd(-C(NH-
tBu)=CH-C(O)Ph)Cl(PPh3)2]
(17), and reacts with Ag[CF$03]
cis-[Pd2(lt-CH2COPh)2(PPh3)41*2[CF3S031 were obtained using crystallographic
in acetonitrile
to give the dimer
(18). The solid state structure of both (17) and (18)
methods [ 151. Ph
Ph3P\
/ Pd
Ph 3 Pip”\
07)
/\ c\ Hz
//O
c Ph (18)
PPh 3
414
P. K. Byers/Coordinution
Treatment of the compounds with excess
norbornadiene,
[Pd(Ar)I(PPhg)Z] (Ar = Ph, p-MeO-Ph, p-Me-Ph, m-MeO-Ph)
or reaction
reported to give the complexes
Chemistry Reviews 146 (1995) 409-429
of [Pd(PPh3)4]
[Pd(QHSAr)I(PPh3)2]
with ArI and norbornadiene
[16]. Reaction of truns-[Pd(Me)I(PPh&l
with 2,6-xylyl isocyanide in a 1: 1 molar ratio led to a spontaneous
insertion of isocyanides
the tris-imino product (19) which was structurally characterised by X-ray crystallography H ‘BuNC, ‘\
i
/
of
/N\
H
Al = p-C6H4X X=H, Me, MeO, Cl-, Br(20)
(19)
dinuclear
p-amid0
[(Pd(C&)(PPh3)]2(p-OH)(p-NIR&~X-p)l have been prepared.
,785
Apd\CNtB” Ar
NR
4
series
lAr
,N\
/‘“\ CEFS NR
Two
\
to give
[17].
-CMe
/‘” Ph 3P
has been
palladium(I1)
complexes
of
the
and [(Pd(C&)(‘BuNC)(lt-NHC&tX-p)]z]
form (20)
The solid state structure of (20; X = H) has been established
using X-ray
diffraction [ 181. Reaction of [Pd(PPh3)4] with 2,6-bis(chloromethyl)pyridine two oxidative addition products: Ca,Wbridging
dinuclear (21) and Cafl,Ca
palladium(I1) compounds 1191.
;ga
I
I
PPh 3
PPh 3
PhN
(21) The reaction LiPhN(Y)NPh monodentate
-bridging tetranuclear
:\:;ph
clq&cl Cl-Pd
in toluene at 1OO’C afforded
(22)
of [PdX2L2] (X = Cl, Br, mesityl;
(Y = N, C(Ph)] (22), didentate
JAN
has been studied.
(23 )
L = PEt3, PMezPh,
PPh3, PEt3) with
For Y = N, the triazendio
(23) and bridging (24) complexes,
ligand forms
whilst for Y = C(Ph) complexes
containing the bridging amidino group (25) were obtained [20]. Resolution of the chiral didentate bis(phosphine) crystallisation
of a pair of diastereomeric
an orthometallated
ligand (26) has been achieved by fractional
palhadium(II) complexes containing the racemic ligand and
(S)-dimethyl(l-phenylethyl)amine
(27). The absolute configuration
enantiomer of the ligand was assigned by a X-ray crystal structure determination
of the (S)-
of (R,S)-(27) 1211.
P.K. Ryers/Coordination
415
Chemistry Reviews 146 (1995) 409-429
Ph (25 )
(24 ) Me?
Ph
Me
+ (26)
dimethylpalladium(I1)
The dimethylpalladium
species
crystallography
complex
complexes,
also reacted
rrans-[PdMe(OCOOR)L2]
of the dimeric
carbamate complexes
R, R’= H, alkyl, phenyl) have been reported.
from the corresponding compounds
I
(w-(27
A series of mm- and cis-methylpalladium = tertiary phosphine;
Ph,
[PdMe(OCONRR’)L2]
The complexes
(L
were prepared
a primary or secondary amine and CO2.
with alcohols
and CO2 to afford alkyl carbonate
(R = Me, SBu; L = PMe3, PPh3). The solid state structure
[Pd2Me2(It-OCONEt2)2(PMe3)2]
(28) was determined
by X-ray
[22]. Et2 N 0
/+-0 “;<
0
\
I Pd I\
Pd
PMe 3
Me
I\ Me,P
Me (28 1
Treatment
of [PdC12(dppe)] with PhSH in the presence of BtqN, or oxidative addition of
PhzSe2 to [Pd(QH4)(dppe)] report, complexes synthesised
gave the complexes
[Pd(EPh)2(dppe)]
of the general formula cis-[M(SCgFg)2L2]
from cis-[MC12L2] and T&SC&)
The p-hydroxo-complexes from reaction of NBqOH
(E = S, Se) [23]. In a similar
(L2 = dppm, dppe, 2PPh3) were
[24].
[ (PdR(PPh$(F-OH))21
with the corresponding
bridged species with pyrazole or 3,5dimethylpyrazole
(R = C6F5, C&15) have been prepared
l,t-chloro compounds.
Reaction of the hydroxo
afforded the new compounds
(29) and (30),
P.K. B.yers/Coordination
416
whilst reaction with oxalic &Ox)
Chemistry Reviews 146 (1995) 409-429
and acetic (HOAc) acids gave dinuclear [(PdR(PPh$)z(p-Ox)1
and [(Pd(C6F5)(PPh3)(~-oAc)l21 WI.
Ph,P
Ph JP
CsFs \
/N-N\
/
C,F5 1
/N-N\
/
/Pd\,lPd\
PPh,
C,F5
(29)
(30)
The solid states of the complexes monothioacetylacetonate) the new compounds phosphinoethane)
[PdMe@dik)(PPhg)]
(31) have been determined [Pd(H2-dmsucc-S,S’)(L-L)]
(L-L = dppe,
into the Pd-H bond,
(Me2NCS2)(PEt3)]
1-diphenylarsino-2-diphenyl-
with LiHBEt3 at low temperature
e.g. reaction
[28]. In a related
with CHz=CHCN
report,
affords in situ the
(33). This species readily inserts alkenes and preparation
(X = Cl, Br) from hydrogenolysis
gives
[Pd(CH(CN)CH3}-
of the hydride
complexes
of trans-[PdX(COPh)(PPh3)2]
x=o,s
(32)
E=P,As
trunk-
was described
WI.
(31)
or
1261, and
(32) have been reported [27].
Reaction of [Pd(Me2NC$)(Cl)(PEt3)]
[PdH(X)(PPh3)2]
(P-dik = acetylacetonate
by single crystal X-ray diffraction
unstable hydrido species [Pd(H)(Me2NCS2)(PEt$] alkynes
PPh 3
H
(33 )
P.K. Byers/Coordination
Treatment of the diphosphine Na2[PdCl4] gave the macrocyclic
Chemistry Reviews 146 (1995) 409-429
417
ligand bis[4- (2-(diphenylphosphino)ethyl)phenyl]ether
compound
(34), apparently
process [30]. Reaction of the anions [Ph2P(Y)PPh2]-
from a spontaneous
with
self assembly
(Y = CH, N) with [PdX2L2] (X = Cl, Br; L =
PPh3, PMezPh, PEt3) complexes has been reported to give a variety of products. Thus, with Y = CH derivatives
[PdCl(Ph2PCHPPh$L]
and [Pd(Ph2PNPPh2)2] the corresponding potentially
cationic complexes
tridentate
afford complexes
were obtained, whilst with Y = N, [PdX(Ph2PNPPh2)(PEt3)]
were isolated. Subsequent treatment of these complexes containing
ligand HC(PPh2)3 coordinates
with HBF4 yielded
the neutral ligand Ph2P(YH)PPh2 to palladium(B)
of the form [PdXX’(t$-(PPh&CH]]
[31]. The
via two of its PPh2 sites to
(X = X’= Cl, Br, C&F5: X = Cl, x’ = CgF5)
t321.
I\
(H ,C=HC)Ph
2P
,I,
,PPh
,(CH=CH
*)
/‘“\,/‘“\,
(35 ) The unexpected product (35) was obtained upon oxidative addition of 12 to the palladium(I) complex
[(Ph2PCH2CH2)&-q3-Ph2PCH$ZH2)Pd]2[BF4]2,
established low-ligated
by X-ray crystallography palladium(O)
[33]. The mechanism
and its solid state structure
was
of oxidative addition of arylhalides to
species, PdOL2 (L = e.g. PPh3). formed by reduction
of their divalent
precursors has been reported 1341. 11.2.2
Complexes with nitrogen donor ligands
Rapid successive,
stoichiometric
the Pd-C bonds of [PdMeClL]
insertions of CO and norbomadiene
(R’CH=CHR”) into
(36) leading to stable products of the type [PdC(O)CH(R’)CH(R”)-
C(O)Me] (37) have been reported [35]. In a similar report, insertion of CO and norbomene Pd-C bond of [Pd[C(O)Me)I(bpy)]
has been described [36].
(361
(37 )
Reaction of [PdC12(bpy)] with LiOMe under a CO atmosphere compound
[Pd(C02Me)2(bpy)].
[Pd(OMeh(bpy)], [Pd(QF5&2)]+
Evidence
for the apparent
was obtained in situ by NMR spectroscopy complexes
into the
gave the bis(carbomethoxy)
precursor
to this complex,
i.e.
[37]. The reactivity of cis- and tray
towards dienes has been reported. The c&complex
[Pd(C&F5)(bpy)]+
P.K. Byers/Coordinarion
418
reacts with dienes [Pd(C&)L2]+,
Chemisrty Reviews 146 (IY95) 409-429
to afford (CgFg-allyl)palladium
derivatives,
e.g. (38). However,
trans-
under similar conditions, failed to give analogous products [38].
N = 2,2’-bipyridine N
Ws Me
(3’3)
A series of (r13-C3Hg)palladium(II) didentate,
bis(chiral-pyrazolyl)
second series of (rlx-allyl)paIladium(II) (40), were investigated dimers
with
complexes,
[Pd(t13-C3Hs)(L2)][PF6],
ligands, e.g. (39), have been prepared complexes containing
using IH NMR spectroscopy
di-2-pyridylsulfide
(dps)
[Pd(~3-allyl)(dps)][Pd(r13-allyl)C12]
containing
[39]. In a related article, a
chiral, bis-(oxazoline)
ligands, e.g.
[40]. Reaction of ($-allyl)palladium
afforded
the
series
of
ionic
in which the dps ligand adopted an N,N’-binding
solid state structure of the complex with ally1 = 2-propenyl was determined
chloride
compounds mode. The
using single crystal X-
ray diffraction [41].
(39 ) Oxidative afforded
(40 )
addition of 2-(2-bromophenyl)ethanol
+ ) ) PI
the arylpalladium(I1)
subject of an X-ray diffraction [Pd( C6H4(CH2CH20H):2) [Pd{C&I&H$TH20))(tmen)]
to [Pd(dba)z]
complex
study.
in the presence
[PdBr[ C~HJ(CH~CH~OH)-~)(~~~~)],
Halide abstraction
(tmen)]N03
(41), which was deprotonated
/N
OJd\ H
(41)
N
= tmen
N
N
which was the
using AgN03 gave the ionic complex
[42].
0
of tmen
using KOMe to yield
P.K. Byers/Coordinarion
NC
CN
NC
CN
419
Chemistry Reviews 146 (1995) 409-429
N\
/
NC
NC
= en
N
(Y3)
(42 )
The neutral, planar complex [PdL2] (42) has been described, along with the crystal structure of its 1,2_dimethoxyethane
adduct [43]. Treatment of 1,2-bis(4-pyridyl)ethane
in a 1:l molar ratio gave the macrocyclic, confirmed by X-ray crystallography The formation
complex (43), the structure of which was
[44].
of palladium(H)
been studied by microcalorimetry
dipalladium
with [Pd(en)][N03]2
complexes
of [18]aneNg,
[2l]aneN7
and tH and 13C NMR spectroscopy.
and [24]aneNg has
Crystals of the dinuclear
Pd2+ complex of [24]aneNg were obtained, and were the subject of an Xray diffraction The synthesis
and structural
characterisation
of [PdL][PF&
reported [46]. The preparation of (terpyridine)palladium(II)
containing
study [45].
cation (44) has been
complexes of phenylcyanamide
anion
ligands, e.g. (45), has been reported, and for (45) the solid state structure has been determined X-ray crystallography
by
[47].
(44 ) The palladium(H)
complex (46) has been reported.
The NMR spectral data indicated that
the complex possessed a weak Pd----Fe dative bond, and this was supported by an X-ray analysis of the complex [48].
420
P.K. &ws/Coordination
Chemistry
Reviews146(1995)409-429
(46 )
Treatment of [PdMe(Cl)(cod)] with the ligands (47) afforded compounds of the type [PdMe(Cl)(N,N’-47)]+, e.g. (48), while ionic compounds of the form [PdMe(N,N’,N”-47)]+, e.g. (49), were obtained by halide abstraction of the chlorides using silver(I) salts [49]. The tridentate and didentate coordination behaviour of N-(2_hydroxyethyl)- 1,2-ethanediamine, L, with PdX2 (X = Cl, Br), and their N,N’,O to N,N’ isomerisation behaviour, has been studied using a variety of techniques. One of the isomers, [PdC12(L)J, has been characterised by single crystal X-ray analysis where the palladium was shown to possess the N2C12donor set [50]. The synthesis and solid state structures of [PdClz(L)] and the palladium(I1) dimer [(L)ClzPdPdC12(L)12+(L = H[9]aneN3; 50) have been reported [51]. H N’
+ Hfi
IN\ H
H
(50) I 12.3
Cyclometallationcomplexes
The first examples of optically active, cyclopalladated primary amines were reported. Thus, reaction of [PdClz( NI&CH(Me)Ph)2] with AgC104, followed by addition of neutral ligands (L2 =
P.K. Byers/Coordination
Chemistry
2py, cod, bpy) or NaBr led to the isolation [(Pd{C6H4[CH(Me)NH2-2])(~-Br))2]
Reviews
of [Pd(CgH4[CH(Me)NH2-2]](L2)]C104
respectively.
Some of the complexes
optically pure by employing (R)-(+)- or (S)-(-)-a-methylbenzylamine In a separate report, the first orthopalladation Treatment [Pd(OAc)2]3
421
146 (1995) 409-429
or
were obtained
as the starting material [52].
of unsubstituted benzylamine was described [53].
[ 1,4-(CyN=CH)2CgHq]
of N,N-terephthalylidenebis(cyclohexylamine) dimer (51), possessing
gave the monocyclopalladated
with
a free formyl group on each
phenyl ring. Complex (51; X = 02CMe) was reacted with halide ions to form (51; X = Cl, Br, I), and (51; X = Cl, Br, I) with Tl(acac) to give (52) or with tertiary phosphines to give (53) [54].
(51) Cyclometallation
(52) of N-benzyl
[Pd(OAc)2]3 has been investigated. aromatic
ring is formed
(53 )
and N-(phenylethyl)-ol-benzoylbenzylideneamines
A five membered endo-metallocycle
in all cases.
The solid state structure
[Pd(Cd_I4(Cd_15C=O)C=NCH(Me)CgHg)(O=SMe2)Cl] of new terdentate
C,N,N’-bound
with
involving the less activated of one of the derivatives
has been established
aryl, benzyl and alkyl organopalladium
[55]. The synthesis compounds
has been
reported, e.g. (54). By attention to ligand design, palladation can be directed towards sp2 and sp3 C-H activation and towards 5-membered or 6-membered ring formation [56]. The
reaction
of
[Pd(OAc)2]3
C6RmH5-mCH=N(CH2)pC6R’nHS_n macrocycles
from C(aromatic)-H
and
has been studied. and C(aliphatic)-H
C(aromatic)-Cl
bipyridine),
imines
(55), has been described.
The deprotonated
X
general
formula
and 6-membered
endo-
were obtained. The
complexes formed by oxidative addition of
bonds [57]. The preparation of cyclometallated
atoms and a carbon of the tbutyl group [58].
of
activation, respectively,
account also reported the formation of cyclopalladated o&o
the
Five-membered
[PdLCl] @IL = 6-Butyl-2,2’-
bipyridine is tridentate through the two N
422
P.K. Byers/Coordination
Chemists
Reviews 146 (1995) 409-429
R
(56)
Ph2
lP\
CY 1
.N_
R
CY (58)
In two related reports,
treatment
MeOC&C(H)=N-2’,4’,6’-Me$&; acetate gave the corresponding into the analogous
of Schiff bases (e.g. 4-MeCeHdC(H)=NCy;
2,4-RzC&I$(H)=NCy cyclometallated
halo-bridged
acetate-bridged
11.2.4
to give mononuclear, e.g. (57), and dinuclear,
[59,60].
Complexes with sulfur donor ligands
Treatment of &[Pd(SZC202)2] afforded the compound
with 2-methylpyridinium
(HC&I7N)2[Pd(S$Z202)2]
(‘S2c’ = 1,3-imidazolidinyl-N,N’-bis(2-benzenethiolate) synthesis
complexes which could be converted
species upon reaction with NaX, e.g. (56). These dimers were
subsequently reacted with a variety of bis(phosphiies) e.g. (58), complexes
3-Me-4-
(R=Me, OMe)], with palladium(II)
from [PdC12(cod)],
hydrochloride
[61]. The palladium(I1) complex [Pd(‘S2C’)]2 (59) has been prepared
1,2-ethanediamine-N,N’-bis(2-benzenethiolate)
Reaction of (59) with pyridine gave [Pd(py)(‘$C’)]
(59 )
in aqueous solution
(60) [62].
(60 )
in a one pot
and CH(OEt)x.
P.K. Byen/Coordination
11.2.5
423
Complexes with mixed donor Iignnds
The neutral dimer complexes containing
the bridging
containing
[SPPh$
[SPPh2]- as a P,S-chelate
[ (Pd(p-SPPh2)(C&)(PPh3))2] diffraction
Chemistry Reviews 146 (I 995) 409-429
[(Pd(p-SPPh2)(C&,)(PR3)]2] ligand, and cationic
(61) (PR3 = PPh3, PPh2Et)
complexes
[Pd(SPPh2)(PPh3)2]+
have been reported. The crystal structures of two of these,
and [Pd(SPPh2)(PPh3)2]C104,
have been established
methods [63]. The thioyl and selenoyl compounds
as chelating didentate ligands, and form complexes
PhzPN(Ph)PPhz=E
state structure of [PdC12[~h2PCH2CH$S(O)Me)]
using X-ray
(E = S, Se) act
[PdClz(L)] containing the Clz(P-S) and C12(P-
Se) donor set [64]. The synthesis of [PdCl2(kPh2ECH2CH$S(O)Me}]
(E = As, P) and the solid
have been described [65].
Ph, Ph3P\pd
/P
Ph 3 P’
‘S
I I
1 +
(621
(61) Neutral and cationic allyl-palladium(R) [Ph2P(CH2)&02]-
(62)
complexes
(n = 1 to 3) or Ph2P(CH2)&02R
For the neutral allyl-palladium
containing
the P,O-didentate
ligands
(n = 1 to 3; R = Me, Et) have been reported.
complexes containing the ligands [PhZP(CH2)aC02]-
(n = 1,2) the
solid state structures were established using X-ray diffraction methods [66]. Reaction of the sodium phosphinopyrazolonate chelate complexes crystallographically
(63) with [Pd(o-CeH4CH2NMe2)(p-C1)]2
(64) and (65). respectively.
The molecular
and [Pd(acac)2]
yields the
structure of (65) was determined
[67]. Optical resolution of the asymmetric chelate (5)[Ph2ECH2-CH$S(O)Me]
(E = As, P) via fractional crystallisation containing ortho-metallated
of a pair of diastereomeric
(S)-( l-(dimethylamine)ethyl]naphthalene
(63 )
(64 )
The preparation
of a new ferrocenylaminophosphine
palladium(R)
complex cations
has been reported [68].
(65 )
ligand (66) has appeared along with
the synthesis and solid state structure of its palladium dichloride complex [69]. The preparation of the valine-derived ]711.
chiral (L)P,iV-didentate
ligand (67) and its PdC12 complex has been reported
424
Chemisry Reviews I46 (1995) 409-429
P.K. Byers/Cmrdination
(66 1
(67 )
(68) Treatment of [Pd(n3-CH$Z(Me)CH2) new compound cis-[Pd(tBuNC)z(Ph2Ppy)Cl2] is monodentate
through phosphorus
(PhzPpy)Cl]
with cis-[Pd(tBuNC)$12]
affords the
in which the potentially didentate PJV-donor ligand
only [71]. A series of new P,N-didentate
ligands capable of
truns chelation have been prepared. The ligands o-Ph2PC&CH2O(CH&C$ktN-2 (68), when treated with Na[PdQ] complexes
When n = 1, cis complexes
[PdC12(o-Ph2PC6H4CH2O(CH2),CgHqN-2)].
formed, but with longer bridges (n = 2.3) rruns-complexes
has been reported [73]. A series of methionine
([9]aneNS2 = 1,4-dithia-
complexes
Cl, Br, I; L = D-, L- or DL-methionine; dmp = 2,6-dimethyl-4H-pyran-4-one) reaction of PdX2 with methionine L)]*dmp was determined (69)
has
been
[PdXzL]*dmp
(X =
have been prepared by
in the presence of dmp. The solid state structure of [PdIz(DL-
using X-ray crystallography
described
were
were the main products [72].
The solid state structure of the complex [Pd([9]aneNS2)2][BF&, 7-azacyclononane)
(n = 1 to 3),
or [PdC12(PhCN)2] in an equimolar ratio gave mainly the 1:l
[75].
[PhSNC(MeC6H4)N=NC(MeC6H4)NSPh]
[74]. The synthesis and crystal structure of
Treatment in toluene
of produces
[Pd(PPh3)4]
with
trans-
(70), in which the ligand is
bonded to palladium in an NSJ’,S-tridentate fashion [76].
(70 ) Ar=4-Me&H,
(69 ) A series of ($-allyl)paUadium(II)
derivatives of chiral N,O-didentate
synthesised to assess their potential as model intermediates
ligands (71) have been
for regio- and stereo-controlled
catalytic
PK. Byers/Coordinntion
425
Chemistry Reviews 146 (1995) 409-429
allylic alkylation and substitution reactions. Crystals of the complex [Pd(r13-cyclohexenyl)[A’-(amethylbenzyl)salicylaldimine)] crystallography
were obtained
as a single
isomer
and subjected
[77]. Reaction of the ligand N-(2-pyridyl)-3-phenyl-2-propene
to X-ray
amide (N-O) (72)
with PdCl:! gave [PClz(N-0)2], in which only the pyridyl nitrogen was coordinated [78].
R’
R20H RQq9
0
oz
q
0
R3 (72 )
(71)
PALLADIUM(I)
11.3
Redox condensation
of [Pdz(dba)g] with [PdClz(PhCN)2]
(R = Me, Ph) gave the dinuclear complexes 3tP NMR spectroscopy, [79]. Electrolysis
and confirmed
of the complexes
in the presence of RN[P(OPh)2]2
(73). The structures have been deduced from tH and
by single crystal X-ray diffraction
[Pd(P_P)(RNC)2][PF&
P-P = dppm, dppe, dppp, dppb) afforded the dinuclear palladium(I)
species (74); for (74; R = 2,6-
Me2HgH3; P-P = dppm) the solid state structure has been determined
t801.
studies on (73; R = Ph)
(R = 2,6-Me2 or 2,4,6-Me3-phenyl; by X-ray crystallography
a (PhO) ‘5’
‘PfOPh), -Pd-Cl
Cl--d I (PhO)
OF’\
I N,
WJW,
R (74 )
(73 ) Treatment arenediazonium containing
of the A-frame
precursor
salts [~-YCSH~N~][BF~]
a symmetrically
bridging
[Pd212(dppm)z(~-Nz-p-C6H4Me)l[BF41 determined
complexes
[Pd2X2(dppm)2]
(Y = H, Me, OMe, F, N@) arenediazenido
ligand.
The
(X = Cl, Br, I) with afforded crystal
1:l adducts structures
and [Pd2C12(dppm)2(~-N2-p-C6H4F)l[BF41
of
were
[81]. Two unusual cationic palladium(I) dimers containing bridging PtBu2 and terminal
PHlBu2 ligands have been reported. The fist of these, (75). contains a Pd-H-P bridging unit, whilst the other, prepared from (79, possesses state structure
was determined
terminal CO ligands (76). For both complexes
crystallographically
[82]. In a separate,
the solid
but related report, (75)
P.K. Byers/Coordination
426
Chemistry
Reviews
146 (1995)
reacted with excess isoprene to yield (77), which was characterised NMR spectroscopy
409-429
+
co
co
I R,HP -Pd
+ 1
using X-ray diffraction
[83].
I -
Pd - PHR2
\/ 92 L
(76)
and
+
R=‘Bu
(77)
A series of dinuclear palladium(I) complexes containing a bridging q3-indenyl been described. indenyl
The complexes
[84]. The preparation
containing a P,O,N-tridentate
ligand have
(78) were prepared from reaction of [PdC12(RNC)2] with lithium and crystallographic
structure
of a cationic
palladium(I)
dimer
ligand has been reported. The complex, (79), possesses an extremely
short Pd----Pd bond [2.500( 1) A] [85].
RNC
(79 )
(78 ) 11.4
PALLADIUM(O)
The preparation MeC(CHzPPh2)3) secondary phosphines
and single
crystal
have been reported
X-ray
analysis
of [Pd(CO)(triphos)]
[86]. The first palladium(O)
as ligands, [Pd(PtBtqH)3],
complex
{triphos
containing
=
only
has been prepared by treating [Pd($-C5Hs)($-
P.K. Byers/Coordinarion
Chemistn:
CgHg)] with P~BLQH [87]. The photolysis
427
Reviews 146 (1995) 409-429
(at 254 nm) of the palladium oxalate [Pd(C204)(dcpe)]
afforded, in high yield, the dinuclear palladium(O) complex (80). The solid state structure of (SO) has been determined,
and possesses a very short Pd----Pd distance of 2.761 l(5) 8, [88].
Ph2
(81)
(80) A range of mixed bisphosphine complexes
have been characterised
one equivalent phosphine
of a chelating
has been established
of palladium(O)
by 31P NMR spectroscopy
phosphine
ligand (P) affords complexes
[Pd(dba)(dppe)]
complexes
of the form [Pd(dba)(P-P)]
by X-ray diffraction
as determined by crystallography
and the
[89]. Treatment of [Pd(dba)z] with
ligand (P-P), or two equivalents
of a monodentate
(81). The crystal structure of
[90]. Buckminsterfullerene,
treated with [Pd(PPh3)4] gave a high yield of [Pd(Ca)(PPh3)2], q2-fashion,
has been prepared
Cm, when
in which fullerene is ligated in an
[91].
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ELSEVIER
11.
Peter
409-429
Palladium
1993
K. Byers
CONTENTS INTRODUCTION .................................................................................................... 409 11.l PALLADIUM(IV) ............................................................................................ 409 11.2 PALLADIUM(I1) ............................................................................................. 410 11.2.1 Complexes with phosphine donor ligands ................................. 410 11.2.2 Complexes with nitrogen donor ligands .................................... 417 11.2.3 Cyclometallation complexes ......................................................420 Complexes with sulfur donor ligands ....................................... 422 11.2.4 Complexes with mixed donor ligands ....................................... 423 11.2.5 11.3 PALLADIUM(I) .............................................................................................. 425 11.4 PALLADIUM(O) .............................................................................................. 426 REFERENCES .......................................................................................................... 427
INTRODUCTION
The coordination chemistry of palladium reported during the year 1993 has been reviewed. Although this account does not intend or claim to be comprehensive, examples have been selected to represent important features. Only the primary journals are covered and were searched for both palladium (and related) as a keyword and being present in the title. The review covers the chemistry of palladium in its 0 + +4 oxidation states, but does not include the catalytic activity of palladium complexes or complexes containing only Pd-C bonds. Classification of the complexes is according to the oxidation state and donor atom. For complexes containing mixed donor sets the priority ordering P>N>S applies, and neutral donors have priority over charged donor atoms; mixed donor didentate ligands are treated separately. 11.1
PALJADIUM(IV)
The new palladium(W)
complex
(1) has been prepared by oxidative
addition of
p-nitrobenzyl bromide to the corresponding parent di-organ0 species. In solution, benzyl group migration to the aromatic site slowly occurs with complete regioselectivity, and with a concomitant decrease in the palladium oxidation state [ 11. OOIO-8545/95/$09.500 1995 Elsevier Science S.A. All rights nxerved SXN OOlO-8545(95)01205-5
410
P.K. Byers/Coordin&m
Palladium(IV)
complexes
subjected to Electrospray
Chemistry Reviews 146 (1995) 409-429
containing
Mass Spectrometry.
ligands such as those displayed
in (2) have been
In the majority of cases, the intact ion was observed
as the base peak at low ion source energies. At higher source energies the palladium(IV) compounds all underwent facile reductive elimination of two methyl groups, as expected [2].
11.2
PALLADIUM(IIJ
11.2.1
Complexes withphosphine
Reaction of [PdX2(PR3)2] EBtt$Itt]
donor ligands
(X = Cl, I; PR3 = PPh3, PMePh2, PMe2Ph) with the nido-[7-
CE=Se, Te) anions has been reported [3]. In thf at ambient temperature twelve vertex [2,2-
(PR3)2-cZoso-2,1-PdEBl~l0]
(3) is obtained, whilst in refluxing toluene reaction produces only
[2-X-2-(PPh3)-cZoso-2,1-PdTeBlgHg(PPh3)]
(4). Further reaction of (4) (X = I) with HgII salts
affords [2-X-2-(PPh3)-cZoso-2,1-PdTeBt&(PPh3)]
(X = Cl, Br, CN, SCN or 02CMe) complexes
(4). The solid state structure of (3; PR3 = PMe2Ph) and (4; X = 02CMe) were determined X-ray diffraction
(H20)-2-(PPh3)-cZoso-2,l-PdTeBtoHg(PPh3)][BF4] determined
using
methods [4]. Further, (4; X = I) when treated with AgBF4 in toluene gave [2(S), whose solid state structure has been
by single crystal X-ray diffraction.
The Hz0 molecule of (5) can be replaced by a
variety of ligands to produce cationic complexes
[2-L-2-(PR3)-closo-2,1-PdTeB$-I9(PPh3)l[BF4l
(L = e.g. CO, CNBu’, NCMe, OC4H8. SC4Hg) (5). In the case of (5; L = CO) the solid state structure of the molecule has been determined by X-ray crystallography In a related report, [PdClz(PMe2Ph)2] dianions to produce the bis(phosphine)palladium
reacted with the nido-[7,8-E2BgHg]2diheteroboranes
(6) were obtained, and their solid structures subsequently
t51.
[4]. (E = As, Sb)
(6). Crystals of the complexes
determined
by X-ray diffraction
studies
P.K. Byers/Coordination
Chemistry Reviews 146 (1995) 409-429
w+
(4)
(3)
. = B-H
. =B-H E=As,Sb
PhMep P The preparation has been reported, derivatives
/‘“\
PMe ,Ph
of [Pd(p-Br)2&][NBu&
and these complexes
(6)
and [PdR2(NCMe)21 (R = p-MeCeH602CH2)
have subsequently
of general formula [PdBrR2L][NBu4]
been used to prepare
convenient procedure for the synthesis of the dinuclear methylpalladium(I1) CI)(PR3)2]
(PR3 = PEt3, PBu3, PMezPh,
complexes
PMePh2 and PPh3) (7) has appeared.
involves reaction of [PdCl&-C1)2(PR3)2]
with SnMe4 in benzene at room temperature.
(7) react with pyrazoles
of base to give the pyrazolato-bridged
in the presence
Both (7) and (8) adopt a trans-configuration
u3P\A jMe M ,/‘“\,
a series of
and [PdRzLT] (L = e.g. PR3, 4-Mepy)
[PdzMeZ(pThe method The dimers
compounds
[7].
6
R3P
1
/N-N\
Me /
‘Y PR3
PR3
(7)
(8)
[7]. A
(8).
P.K. Byers/Coordination
412
Thermolysis
Chemisrv
Reviews
of the dimer [Pd$12( ~-tBu2P(CH2)sPtBu2)2]
X = Cl) containing the P,C,P’-tridentate
protonated
with [HNMe3][BF4]
complex is readily displaced by coordinating [Pd(H20)L][BPb]
409-429
readily affords the complex (9;
ligand (L). Metathesis of this complex with MeLi or LiAELt
produces the analogous methyl and hydride complexes can be selectively
146 (1995)
solvents.
(9; X = H, Me), and complex (9; X = Me) to yield [Pd(BFd)L];
the BF4 ligand in the
The solid state structures of [PdMe(L)] and
were determined using X-ray diffraction methods [8].
Pd-P PBu t2 I
But2
x
X=Cl,H,Me (9)
Treatment with base of n-allylpalladium 2-position
complexes bearing a methoxymethoxy
has been reported to give the corresponding
contrast to the formation of 2-hydroxy-substituted
oxodimethylenemethane
group at the
complex (10) in
tt-alkyl complexes (11) via acidic hydrolysis [9].
0
(10)
(11)
A series of cyclopentadienyl
complexes
of the type [Pd(tl5-C5H5)(CH2Z)(PPh3)]
COPh, COMe, COCH2C1, CN, SMe) (12) have been prepared and characterised. all react with dry HCl to give [Pd(q%sHs)Cl(PPh3)] [PdC12(PPh3)]2
[ 101. The palladium
triflate complexes
and finally dimeric
[Pd(OTF)z(P-P)]
(P-P = dppm, dppe,
characterised
(13); the solid state structure of (13;
using X-ray diffraction methods [ 111. Cyclopentadienylpalladium(I1)
complexes have also been obtained by with [Pd2Ph2(FL-OH)2L2]
The complexes
as an intermediate,
dppp) react with Tl(CsHs) to produce the cationic complexes P-P = dppe) was determined
(Z =
direct
reaction of cyclopentadiene
(L = PPh3, PCy3). The complex
by single crystal X-ray diffraction [12].
or methylcyclopentadiene
(14; L = PPh3) was structurally
P.K. Byers/Coordination
Chemistry
I
square planar cis-alkyl(carbony1)
spectroscopy complexes
(14)
[13]. The insertion
was
(15) has been described.
prepared
((S,S)-BDPP
by halide
of CO, and was identified
of isocyanides
affords new (metallovinyl)ketenimine
transition metal complex containing a chelating
[Pd(Me)(CO)((S,S)-BDPP]][BF4]
(2S,4S)-2,4_bis(diphenylphosphino)pentane] in the presence
413
PhAPd\L
(13)
has been reported. The complex,
[PdMeCl((S,S)-BDPP)]
409-429
I
p/pd\p
PPh 3
(12)
Thejirst
146 (1995)
I
ZH 2CApd\
diphosphine
Reviews
abstraction
=
from
using high pressure
NMR
into the M-C bond of (o-allenyl)palladium(II)
When the R groups on the allenyl ligand are small, insertion compounds
rrans-[PdX[
C(CRR’)(CH=C=NR”))
(PPh3)2]
(16) 1141.
-
The complex PhCOCH2Cl palladium.
Ph3P
[Pd(CH2COPh)(Cl)(PPh3)2]
to [Pd(PPh&],
has been prepared
and X-ray analysis has revealed
X
by oxidative
addition of
the enolate to be C-bonded
to
The complex inserts a tBuNC molecule into the Pd-C bond to form trans-[Pd(-C(NH-
tBu)=CH-C(O)Ph)Cl(PPh3)2]
(17), and reacts with Ag[CF$03]
cis-[Pd2(lt-CH2COPh)2(PPh3)41*2[CF3S031 were obtained using crystallographic
in acetonitrile
to give the dimer
(18). The solid state structure of both (17) and (18)
methods [ 151. Ph
Ph3P\
/ Pd
Ph 3 Pip”\
07)
/\ c\ Hz
//O
c Ph (18)
PPh 3
414
P. K. Byers/Coordinution
Treatment of the compounds with excess
norbornadiene,
[Pd(Ar)I(PPhg)Z] (Ar = Ph, p-MeO-Ph, p-Me-Ph, m-MeO-Ph)
or reaction
reported to give the complexes
Chemistry Reviews 146 (1995) 409-429
of [Pd(PPh3)4]
[Pd(QHSAr)I(PPh3)2]
with ArI and norbornadiene
[16]. Reaction of truns-[Pd(Me)I(PPh&l
with 2,6-xylyl isocyanide in a 1: 1 molar ratio led to a spontaneous
insertion of isocyanides
the tris-imino product (19) which was structurally characterised by X-ray crystallography H ‘BuNC, ‘\
i
/
of
/N\
H
Al = p-C6H4X X=H, Me, MeO, Cl-, Br(20)
(19)
dinuclear
p-amid0
[(Pd(C&)(PPh3)]2(p-OH)(p-NIR&~X-p)l have been prepared.
,785
Apd\CNtB” Ar
NR
4
series
lAr
,N\
/‘“\ CEFS NR
Two
\
to give
[17].
-CMe
/‘” Ph 3P
has been
palladium(I1)
complexes
of
the
and [(Pd(C&)(‘BuNC)(lt-NHC&tX-p)]z]
form (20)
The solid state structure of (20; X = H) has been established
using X-ray
diffraction [ 181. Reaction of [Pd(PPh3)4] with 2,6-bis(chloromethyl)pyridine two oxidative addition products: Ca,Wbridging
dinuclear (21) and Cafl,Ca
palladium(I1) compounds 1191.
;ga
I
I
PPh 3
PPh 3
PhN
(21) The reaction LiPhN(Y)NPh monodentate
-bridging tetranuclear
:\:;ph
clq&cl Cl-Pd
in toluene at 1OO’C afforded
(22)
of [PdX2L2] (X = Cl, Br, mesityl;
(Y = N, C(Ph)] (22), didentate
JAN
has been studied.
(23 )
L = PEt3, PMezPh,
PPh3, PEt3) with
For Y = N, the triazendio
(23) and bridging (24) complexes,
ligand forms
whilst for Y = C(Ph) complexes
containing the bridging amidino group (25) were obtained [20]. Resolution of the chiral didentate bis(phosphine) crystallisation
of a pair of diastereomeric
an orthometallated
ligand (26) has been achieved by fractional
palhadium(II) complexes containing the racemic ligand and
(S)-dimethyl(l-phenylethyl)amine
(27). The absolute configuration
enantiomer of the ligand was assigned by a X-ray crystal structure determination
of the (S)-
of (R,S)-(27) 1211.
P.K. Ryers/Coordination
415
Chemistry Reviews 146 (1995) 409-429
Ph (25 )
(24 ) Me?
Ph
Me
+ (26)
dimethylpalladium(I1)
The dimethylpalladium
species
crystallography
complex
complexes,
also reacted
rrans-[PdMe(OCOOR)L2]
of the dimeric
carbamate complexes
R, R’= H, alkyl, phenyl) have been reported.
from the corresponding compounds
I
(w-(27
A series of mm- and cis-methylpalladium = tertiary phosphine;
Ph,
[PdMe(OCONRR’)L2]
The complexes
(L
were prepared
a primary or secondary amine and CO2.
with alcohols
and CO2 to afford alkyl carbonate
(R = Me, SBu; L = PMe3, PPh3). The solid state structure
[Pd2Me2(It-OCONEt2)2(PMe3)2]
(28) was determined
by X-ray
[22]. Et2 N 0
/+-0 “;<
0
\
I Pd I\
Pd
PMe 3
Me
I\ Me,P
Me (28 1
Treatment
of [PdC12(dppe)] with PhSH in the presence of BtqN, or oxidative addition of
PhzSe2 to [Pd(QH4)(dppe)] report, complexes synthesised
gave the complexes
[Pd(EPh)2(dppe)]
of the general formula cis-[M(SCgFg)2L2]
from cis-[MC12L2] and T&SC&)
The p-hydroxo-complexes from reaction of NBqOH
(E = S, Se) [23]. In a similar
(L2 = dppm, dppe, 2PPh3) were
[24].
[ (PdR(PPh$(F-OH))21
with the corresponding
bridged species with pyrazole or 3,5dimethylpyrazole
(R = C6F5, C&15) have been prepared
l,t-chloro compounds.
Reaction of the hydroxo
afforded the new compounds
(29) and (30),
P.K. B.yers/Coordination
416
whilst reaction with oxalic &Ox)
Chemistry Reviews 146 (1995) 409-429
and acetic (HOAc) acids gave dinuclear [(PdR(PPh$)z(p-Ox)1
and [(Pd(C6F5)(PPh3)(~-oAc)l21 WI.
Ph,P
Ph JP
CsFs \
/N-N\
/
C,F5 1
/N-N\
/
/Pd\,lPd\
PPh,
C,F5
(29)
(30)
The solid states of the complexes monothioacetylacetonate) the new compounds phosphinoethane)
[PdMe@dik)(PPhg)]
(31) have been determined [Pd(H2-dmsucc-S,S’)(L-L)]
(L-L = dppe,
into the Pd-H bond,
(Me2NCS2)(PEt3)]
1-diphenylarsino-2-diphenyl-
with LiHBEt3 at low temperature
e.g. reaction
[28]. In a related
with CHz=CHCN
report,
affords in situ the
(33). This species readily inserts alkenes and preparation
(X = Cl, Br) from hydrogenolysis
gives
[Pd(CH(CN)CH3}-
of the hydride
complexes
of trans-[PdX(COPh)(PPh3)2]
x=o,s
(32)
E=P,As
trunk-
was described
WI.
(31)
or
1261, and
(32) have been reported [27].
Reaction of [Pd(Me2NC$)(Cl)(PEt3)]
[PdH(X)(PPh3)2]
(P-dik = acetylacetonate
by single crystal X-ray diffraction
unstable hydrido species [Pd(H)(Me2NCS2)(PEt$] alkynes
PPh 3
H
(33 )
P.K. Byers/Coordination
Treatment of the diphosphine Na2[PdCl4] gave the macrocyclic
Chemistry Reviews 146 (1995) 409-429
417
ligand bis[4- (2-(diphenylphosphino)ethyl)phenyl]ether
compound
(34), apparently
process [30]. Reaction of the anions [Ph2P(Y)PPh2]-
from a spontaneous
with
self assembly
(Y = CH, N) with [PdX2L2] (X = Cl, Br; L =
PPh3, PMezPh, PEt3) complexes has been reported to give a variety of products. Thus, with Y = CH derivatives
[PdCl(Ph2PCHPPh$L]
and [Pd(Ph2PNPPh2)2] the corresponding potentially
cationic complexes
tridentate
afford complexes
were obtained, whilst with Y = N, [PdX(Ph2PNPPh2)(PEt3)]
were isolated. Subsequent treatment of these complexes containing
ligand HC(PPh2)3 coordinates
with HBF4 yielded
the neutral ligand Ph2P(YH)PPh2 to palladium(B)
of the form [PdXX’(t$-(PPh&CH]]
[31]. The
via two of its PPh2 sites to
(X = X’= Cl, Br, C&F5: X = Cl, x’ = CgF5)
t321.
I\
(H ,C=HC)Ph
2P
,I,
,PPh
,(CH=CH
*)
/‘“\,/‘“\,
(35 ) The unexpected product (35) was obtained upon oxidative addition of 12 to the palladium(I) complex
[(Ph2PCH2CH2)&-q3-Ph2PCH$ZH2)Pd]2[BF4]2,
established low-ligated
by X-ray crystallography palladium(O)
[33]. The mechanism
and its solid state structure
was
of oxidative addition of arylhalides to
species, PdOL2 (L = e.g. PPh3). formed by reduction
of their divalent
precursors has been reported 1341. 11.2.2
Complexes with nitrogen donor ligands
Rapid successive,
stoichiometric
the Pd-C bonds of [PdMeClL]
insertions of CO and norbomadiene
(R’CH=CHR”) into
(36) leading to stable products of the type [PdC(O)CH(R’)CH(R”)-
C(O)Me] (37) have been reported [35]. In a similar report, insertion of CO and norbomene Pd-C bond of [Pd[C(O)Me)I(bpy)]
has been described [36].
(361
(37 )
Reaction of [PdC12(bpy)] with LiOMe under a CO atmosphere compound
[Pd(C02Me)2(bpy)].
[Pd(OMeh(bpy)], [Pd(QF5&2)]+
Evidence
for the apparent
was obtained in situ by NMR spectroscopy complexes
into the
gave the bis(carbomethoxy)
precursor
to this complex,
i.e.
[37]. The reactivity of cis- and tray
towards dienes has been reported. The c&complex
[Pd(C&F5)(bpy)]+
P.K. Byers/Coordinarion
418
reacts with dienes [Pd(C&)L2]+,
Chemisrty Reviews 146 (IY95) 409-429
to afford (CgFg-allyl)palladium
derivatives,
e.g. (38). However,
trans-
under similar conditions, failed to give analogous products [38].
N = 2,2’-bipyridine N
Ws Me
(3’3)
A series of (r13-C3Hg)palladium(II) didentate,
bis(chiral-pyrazolyl)
second series of (rlx-allyl)paIladium(II) (40), were investigated dimers
with
complexes,
[Pd(t13-C3Hs)(L2)][PF6],
ligands, e.g. (39), have been prepared complexes containing
using IH NMR spectroscopy
di-2-pyridylsulfide
(dps)
[Pd(~3-allyl)(dps)][Pd(r13-allyl)C12]
containing
[39]. In a related article, a
chiral, bis-(oxazoline)
ligands, e.g.
[40]. Reaction of ($-allyl)palladium
afforded
the
series
of
ionic
in which the dps ligand adopted an N,N’-binding
solid state structure of the complex with ally1 = 2-propenyl was determined
chloride
compounds mode. The
using single crystal X-
ray diffraction [41].
(39 ) Oxidative afforded
(40 )
addition of 2-(2-bromophenyl)ethanol
+ ) ) PI
the arylpalladium(I1)
subject of an X-ray diffraction [Pd( C6H4(CH2CH20H):2) [Pd{C&I&H$TH20))(tmen)]
to [Pd(dba)z]
complex
study.
in the presence
[PdBr[ C~HJ(CH~CH~OH)-~)(~~~~)],
Halide abstraction
(tmen)]N03
(41), which was deprotonated
/N
OJd\ H
(41)
N
= tmen
N
N
which was the
using AgN03 gave the ionic complex
[42].
0
of tmen
using KOMe to yield
P.K. Byers/Coordinarion
NC
CN
NC
CN
419
Chemistry Reviews 146 (1995) 409-429
N\
/
NC
NC
= en
N
(Y3)
(42 )
The neutral, planar complex [PdL2] (42) has been described, along with the crystal structure of its 1,2_dimethoxyethane
adduct [43]. Treatment of 1,2-bis(4-pyridyl)ethane
in a 1:l molar ratio gave the macrocyclic, confirmed by X-ray crystallography The formation
complex (43), the structure of which was
[44].
of palladium(H)
been studied by microcalorimetry
dipalladium
with [Pd(en)][N03]2
complexes
of [18]aneNg,
[2l]aneN7
and tH and 13C NMR spectroscopy.
and [24]aneNg has
Crystals of the dinuclear
Pd2+ complex of [24]aneNg were obtained, and were the subject of an Xray diffraction The synthesis
and structural
characterisation
of [PdL][PF&
reported [46]. The preparation of (terpyridine)palladium(II)
containing
study [45].
cation (44) has been
complexes of phenylcyanamide
anion
ligands, e.g. (45), has been reported, and for (45) the solid state structure has been determined X-ray crystallography
by
[47].
(44 ) The palladium(H)
complex (46) has been reported.
The NMR spectral data indicated that
the complex possessed a weak Pd----Fe dative bond, and this was supported by an X-ray analysis of the complex [48].
420
P.K. &ws/Coordination
Chemistry
Reviews146(1995)409-429
(46 )
Treatment of [PdMe(Cl)(cod)] with the ligands (47) afforded compounds of the type [PdMe(Cl)(N,N’-47)]+, e.g. (48), while ionic compounds of the form [PdMe(N,N’,N”-47)]+, e.g. (49), were obtained by halide abstraction of the chlorides using silver(I) salts [49]. The tridentate and didentate coordination behaviour of N-(2_hydroxyethyl)- 1,2-ethanediamine, L, with PdX2 (X = Cl, Br), and their N,N’,O to N,N’ isomerisation behaviour, has been studied using a variety of techniques. One of the isomers, [PdC12(L)J, has been characterised by single crystal X-ray analysis where the palladium was shown to possess the N2C12donor set [50]. The synthesis and solid state structures of [PdClz(L)] and the palladium(I1) dimer [(L)ClzPdPdC12(L)12+(L = H[9]aneN3; 50) have been reported [51]. H N’
+ Hfi
IN\ H
H
(50) I 12.3
Cyclometallationcomplexes
The first examples of optically active, cyclopalladated primary amines were reported. Thus, reaction of [PdClz( NI&CH(Me)Ph)2] with AgC104, followed by addition of neutral ligands (L2 =
P.K. Byers/Coordination
Chemistry
2py, cod, bpy) or NaBr led to the isolation [(Pd{C6H4[CH(Me)NH2-2])(~-Br))2]
Reviews
of [Pd(CgH4[CH(Me)NH2-2]](L2)]C104
respectively.
Some of the complexes
optically pure by employing (R)-(+)- or (S)-(-)-a-methylbenzylamine In a separate report, the first orthopalladation Treatment [Pd(OAc)2]3
421
146 (1995) 409-429
or
were obtained
as the starting material [52].
of unsubstituted benzylamine was described [53].
[ 1,4-(CyN=CH)2CgHq]
of N,N-terephthalylidenebis(cyclohexylamine) dimer (51), possessing
gave the monocyclopalladated
with
a free formyl group on each
phenyl ring. Complex (51; X = 02CMe) was reacted with halide ions to form (51; X = Cl, Br, I), and (51; X = Cl, Br, I) with Tl(acac) to give (52) or with tertiary phosphines to give (53) [54].
(51) Cyclometallation
(52) of N-benzyl
[Pd(OAc)2]3 has been investigated. aromatic
ring is formed
(53 )
and N-(phenylethyl)-ol-benzoylbenzylideneamines
A five membered endo-metallocycle
in all cases.
The solid state structure
[Pd(Cd_I4(Cd_15C=O)C=NCH(Me)CgHg)(O=SMe2)Cl] of new terdentate
C,N,N’-bound
with
involving the less activated of one of the derivatives
has been established
aryl, benzyl and alkyl organopalladium
[55]. The synthesis compounds
has been
reported, e.g. (54). By attention to ligand design, palladation can be directed towards sp2 and sp3 C-H activation and towards 5-membered or 6-membered ring formation [56]. The
reaction
of
[Pd(OAc)2]3
C6RmH5-mCH=N(CH2)pC6R’nHS_n macrocycles
from C(aromatic)-H
and
has been studied. and C(aliphatic)-H
C(aromatic)-Cl
bipyridine),
imines
(55), has been described.
The deprotonated
X
general
formula
and 6-membered
endo-
were obtained. The
complexes formed by oxidative addition of
bonds [57]. The preparation of cyclometallated
atoms and a carbon of the tbutyl group [58].
of
activation, respectively,
account also reported the formation of cyclopalladated o&o
the
Five-membered
[PdLCl] @IL = 6-Butyl-2,2’-
bipyridine is tridentate through the two N
422
P.K. Byers/Coordination
Chemists
Reviews 146 (1995) 409-429
R
(56)
Ph2
lP\
CY 1
.N_
R
CY (58)
In two related reports,
treatment
MeOC&C(H)=N-2’,4’,6’-Me$&; acetate gave the corresponding into the analogous
of Schiff bases (e.g. 4-MeCeHdC(H)=NCy;
2,4-RzC&I$(H)=NCy cyclometallated
halo-bridged
acetate-bridged
11.2.4
to give mononuclear, e.g. (57), and dinuclear,
[59,60].
Complexes with sulfur donor ligands
Treatment of &[Pd(SZC202)2] afforded the compound
with 2-methylpyridinium
(HC&I7N)2[Pd(S$Z202)2]
(‘S2c’ = 1,3-imidazolidinyl-N,N’-bis(2-benzenethiolate) synthesis
complexes which could be converted
species upon reaction with NaX, e.g. (56). These dimers were
subsequently reacted with a variety of bis(phosphiies) e.g. (58), complexes
3-Me-4-
(R=Me, OMe)], with palladium(II)
from [PdC12(cod)],
hydrochloride
[61]. The palladium(I1) complex [Pd(‘S2C’)]2 (59) has been prepared
1,2-ethanediamine-N,N’-bis(2-benzenethiolate)
Reaction of (59) with pyridine gave [Pd(py)(‘$C’)]
(59 )
in aqueous solution
(60) [62].
(60 )
in a one pot
and CH(OEt)x.
P.K. Byen/Coordination
11.2.5
423
Complexes with mixed donor Iignnds
The neutral dimer complexes containing
the bridging
containing
[SPPh$
[SPPh2]- as a P,S-chelate
[ (Pd(p-SPPh2)(C&)(PPh3))2] diffraction
Chemistry Reviews 146 (I 995) 409-429
[(Pd(p-SPPh2)(C&,)(PR3)]2] ligand, and cationic
(61) (PR3 = PPh3, PPh2Et)
complexes
[Pd(SPPh2)(PPh3)2]+
have been reported. The crystal structures of two of these,
and [Pd(SPPh2)(PPh3)2]C104,
have been established
methods [63]. The thioyl and selenoyl compounds
as chelating didentate ligands, and form complexes
PhzPN(Ph)PPhz=E
state structure of [PdC12[~h2PCH2CH$S(O)Me)]
using X-ray
(E = S, Se) act
[PdClz(L)] containing the Clz(P-S) and C12(P-
Se) donor set [64]. The synthesis of [PdCl2(kPh2ECH2CH$S(O)Me}]
(E = As, P) and the solid
have been described [65].
Ph, Ph3P\pd
/P
Ph 3 P’
‘S
I I
1 +
(621
(61) Neutral and cationic allyl-palladium(R) [Ph2P(CH2)&02]-
(62)
complexes
(n = 1 to 3) or Ph2P(CH2)&02R
For the neutral allyl-palladium
containing
the P,O-didentate
ligands
(n = 1 to 3; R = Me, Et) have been reported.
complexes containing the ligands [PhZP(CH2)aC02]-
(n = 1,2) the
solid state structures were established using X-ray diffraction methods [66]. Reaction of the sodium phosphinopyrazolonate chelate complexes crystallographically
(63) with [Pd(o-CeH4CH2NMe2)(p-C1)]2
(64) and (65). respectively.
The molecular
and [Pd(acac)2]
yields the
structure of (65) was determined
[67]. Optical resolution of the asymmetric chelate (5)[Ph2ECH2-CH$S(O)Me]
(E = As, P) via fractional crystallisation containing ortho-metallated
of a pair of diastereomeric
(S)-( l-(dimethylamine)ethyl]naphthalene
(63 )
(64 )
The preparation
of a new ferrocenylaminophosphine
palladium(R)
complex cations
has been reported [68].
(65 )
ligand (66) has appeared along with
the synthesis and solid state structure of its palladium dichloride complex [69]. The preparation of the valine-derived ]711.
chiral (L)P,iV-didentate
ligand (67) and its PdC12 complex has been reported
424
Chemisry Reviews I46 (1995) 409-429
P.K. Byers/Cmrdination
(66 1
(67 )
(68) Treatment of [Pd(n3-CH$Z(Me)CH2) new compound cis-[Pd(tBuNC)z(Ph2Ppy)Cl2] is monodentate
through phosphorus
(PhzPpy)Cl]
with cis-[Pd(tBuNC)$12]
affords the
in which the potentially didentate PJV-donor ligand
only [71]. A series of new P,N-didentate
ligands capable of
truns chelation have been prepared. The ligands o-Ph2PC&CH2O(CH&C$ktN-2 (68), when treated with Na[PdQ] complexes
When n = 1, cis complexes
[PdC12(o-Ph2PC6H4CH2O(CH2),CgHqN-2)].
formed, but with longer bridges (n = 2.3) rruns-complexes
has been reported [73]. A series of methionine
([9]aneNS2 = 1,4-dithia-
complexes
Cl, Br, I; L = D-, L- or DL-methionine; dmp = 2,6-dimethyl-4H-pyran-4-one) reaction of PdX2 with methionine L)]*dmp was determined (69)
has
been
[PdXzL]*dmp
(X =
have been prepared by
in the presence of dmp. The solid state structure of [PdIz(DL-
using X-ray crystallography
described
were
were the main products [72].
The solid state structure of the complex [Pd([9]aneNS2)2][BF&, 7-azacyclononane)
(n = 1 to 3),
or [PdC12(PhCN)2] in an equimolar ratio gave mainly the 1:l
[75].
[PhSNC(MeC6H4)N=NC(MeC6H4)NSPh]
[74]. The synthesis and crystal structure of
Treatment in toluene
of produces
[Pd(PPh3)4]
with
trans-
(70), in which the ligand is
bonded to palladium in an NSJ’,S-tridentate fashion [76].
(70 ) Ar=4-Me&H,
(69 ) A series of ($-allyl)paUadium(II)
derivatives of chiral N,O-didentate
synthesised to assess their potential as model intermediates
ligands (71) have been
for regio- and stereo-controlled
catalytic
PK. Byers/Coordinntion
425
Chemistry Reviews 146 (1995) 409-429
allylic alkylation and substitution reactions. Crystals of the complex [Pd(r13-cyclohexenyl)[A’-(amethylbenzyl)salicylaldimine)] crystallography
were obtained
as a single
isomer
and subjected
[77]. Reaction of the ligand N-(2-pyridyl)-3-phenyl-2-propene
to X-ray
amide (N-O) (72)
with PdCl:! gave [PClz(N-0)2], in which only the pyridyl nitrogen was coordinated [78].
R’
R20H RQq9
0
oz
q
0
R3 (72 )
(71)
PALLADIUM(I)
11.3
Redox condensation
of [Pdz(dba)g] with [PdClz(PhCN)2]
(R = Me, Ph) gave the dinuclear complexes 3tP NMR spectroscopy, [79]. Electrolysis
and confirmed
of the complexes
in the presence of RN[P(OPh)2]2
(73). The structures have been deduced from tH and
by single crystal X-ray diffraction
[Pd(P_P)(RNC)2][PF&
P-P = dppm, dppe, dppp, dppb) afforded the dinuclear palladium(I)
species (74); for (74; R = 2,6-
Me2HgH3; P-P = dppm) the solid state structure has been determined
t801.
studies on (73; R = Ph)
(R = 2,6-Me2 or 2,4,6-Me3-phenyl; by X-ray crystallography
a (PhO) ‘5’
‘PfOPh), -Pd-Cl
Cl--d I (PhO)
OF’\
I N,
WJW,
R (74 )
(73 ) Treatment arenediazonium containing
of the A-frame
precursor
salts [~-YCSH~N~][BF~]
a symmetrically
bridging
[Pd212(dppm)z(~-Nz-p-C6H4Me)l[BF41 determined
complexes
[Pd2X2(dppm)2]
(Y = H, Me, OMe, F, N@) arenediazenido
ligand.
The
(X = Cl, Br, I) with afforded crystal
1:l adducts structures
and [Pd2C12(dppm)2(~-N2-p-C6H4F)l[BF41
of
were
[81]. Two unusual cationic palladium(I) dimers containing bridging PtBu2 and terminal
PHlBu2 ligands have been reported. The fist of these, (75). contains a Pd-H-P bridging unit, whilst the other, prepared from (79, possesses state structure
was determined
terminal CO ligands (76). For both complexes
crystallographically
[82]. In a separate,
the solid
but related report, (75)
P.K. Byers/Coordination
426
Chemistry
Reviews
146 (1995)
reacted with excess isoprene to yield (77), which was characterised NMR spectroscopy
409-429
+
co
co
I R,HP -Pd
+ 1
using X-ray diffraction
[83].
I -
Pd - PHR2
\/ 92 L
(76)
and
+
R=‘Bu
(77)
A series of dinuclear palladium(I) complexes containing a bridging q3-indenyl been described. indenyl
The complexes
[84]. The preparation
containing a P,O,N-tridentate
ligand have
(78) were prepared from reaction of [PdC12(RNC)2] with lithium and crystallographic
structure
of a cationic
palladium(I)
dimer
ligand has been reported. The complex, (79), possesses an extremely
short Pd----Pd bond [2.500( 1) A] [85].
RNC
(79 )
(78 ) 11.4
PALLADIUM(O)
The preparation MeC(CHzPPh2)3) secondary phosphines
and single
crystal
have been reported
X-ray
analysis
of [Pd(CO)(triphos)]
[86]. The first palladium(O)
as ligands, [Pd(PtBtqH)3],
complex
{triphos
containing
=
only
has been prepared by treating [Pd($-C5Hs)($-
P.K. Byers/Coordinarion
Chemistn:
CgHg)] with P~BLQH [87]. The photolysis
427
Reviews 146 (1995) 409-429
(at 254 nm) of the palladium oxalate [Pd(C204)(dcpe)]
afforded, in high yield, the dinuclear palladium(O) complex (80). The solid state structure of (SO) has been determined,
and possesses a very short Pd----Pd distance of 2.761 l(5) 8, [88].
Ph2
(81)
(80) A range of mixed bisphosphine complexes
have been characterised
one equivalent phosphine
of a chelating
has been established
of palladium(O)
by 31P NMR spectroscopy
phosphine
ligand (P) affords complexes
[Pd(dba)(dppe)]
complexes
of the form [Pd(dba)(P-P)]
by X-ray diffraction
as determined by crystallography
and the
[89]. Treatment of [Pd(dba)z] with
ligand (P-P), or two equivalents
of a monodentate
(81). The crystal structure of
[90]. Buckminsterfullerene,
treated with [Pd(PPh3)4] gave a high yield of [Pd(Ca)(PPh3)2], q2-fashion,
has been prepared
Cm, when
in which fullerene is ligated in an
[91].
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