Title: Oxidative Addition of 2-Halogenopyridines and 2-Chloroquinoline

to Zero-Valent Group 10 Metals

Authors: Ekkehardt Hahn, Mareike C. Jahnke, and Ramona M. C. Pichl

This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.202000279

Link to VoR: https://doi.org/10.1002/zaac.202000279

Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000279

ARTICLE
Oxidative Addition of 2-Halogenopyridines and 2-Chloroquinoline to
Zero-Valent Group 10 Metals
Mareike C. Jahnke,[a] Ramona M. C. Pichl[a] and F. Ekkehardt Hahn*[a]

Dedicated to Professor Christoph Janiak on the Occasion of His 60th Birthday with our Congratulations and Best Wishes

Abstract: Oxidative addition of the C2−X (X = Cl, Br) bond of 2- reported as early as 1973 by Roper and coworkers.[12]
halogenopyridines or 2-chloroquinoline to zero-valent group 10 The oxidative addition of the C2−H bond of neutral azoles
metal complexes in the presence of a proton source leads to requires the presence of an N-bound donor group. This donor
complexes bearing pyridine-derived protic remote NHC (rNHC) initially coordinates to the metal center and facilitates the

Accepted Manuscript
ligands. The oxidative addition of 2-halogeno-functionalized subsequent addition of the C2−H bond. The intermediately formed
pyridine derivatives to complexes [M0(PPh3)4] (M = Pd, Pt) in the hydrido complex is normally not stable and subsequently
presence of NH4BF4 or NH4PF6 yielded complexes trans- reductively eliminates a proton, which protonates the unsubstituted
[1]PF6‒trans-[5]BF4 with a trans-arrangement of the two ring nitrogen atom leading to the complex with a pNHC ligand.
remaining PPh3 ligands. The oxidative addition to Ni0 was Complexes of type C (Figure 1) bearing various chelating
achieved by reaction of the halogenopyridine derivatives with coordinated pNHC^donor ligands have been obtained by this
[Ni(cod)2]/PEt3 in the presence of a proton acid (NH4BF4 or method.[5a-c,10,13]
NH4PF6) yielding complexes of type trans-[Ni(protic- The oxidative addition of the C2X (X = halogen) bond of
rNHC)(PEt3)2X]A (A = BF4, PF6). In the absence of a proton azolium cations proceeds without the need for an N-tethered donor
source, the oxidative addition of 2-chloroquinone to to yield NHC complexes of type D[14] (Figure 1). For neutral 2-
[Ni(cod)2]/PEt3 yielded the neutral complex trans-[8] bearing an halogenoazoles, azolato complexes E[11a,b] are obtained, which in
anionic quinoline-derived rNHC ligand. The molecular structures the presence of a proton source yield pNHC complexes F.[11a,b,15]
of selected complexes have been determined by X-ray diffraction Even complexes with mesoionic protic NHCs[5d,16] or with C8-
studies. metallated pNHC ligands derived from biomolecules such as
adenine or guanine[17] have been prepared by the oxidative addition
Introduction of halogenoazoles.
Over the last decade, complexes bearing protic N-heterocyclic R n+ R n+ D n+
carbene (pNHC) ligands have gained significant attention.[1] N N N
Contrary to complexes bearing the ubiquitous, classical NR,NR- ML x ML x ML x
N N N
NHC ligands (Figure1, A),[2] the protic carbene ligands (pNHCs) in
R H H
complexes of type B (Figure 1) can subsequently be NH- A B C
deprotonated and modified.[3] Furthermore, the NH function of R = alkyl, aryl R = Me, Et, H
the pNHC ligands can serve as recognition unit in substrate
specific catalytic reactions[4] and several complexes bearing protic R n+ R n+ R (n+1)+
NHCs have also been shown to be capable of small molecule N N N
H+
activation.[5] Access to complexes bearing pNHC ligands is limited ML y MLy ML y
since pNHCs, contrary to free NHCs, are not stable in the N N N
X X X
uncoordinated state.[1] Complexes bearing pNHC ligands are R H
D E F
accessible by the template-controlled cyclization of β-
functionalized isocyanides at a suitable metal center,[3a,b,6] by
+ PPh3
formal tautomerization of N-coordinated azoles after C2- L
deprotonation,[7] by the direct reaction of lithiated azoles with N M
N X
M
suitable metal precursors followed by N-protonation[4a,8] or by the M N
X
R' X
removal of an N-protection group at one of the nitrogen atoms of L
Ph3P
the NHC diazaheterocycle.[9] H
G
Recently, the oxidative addition of the C2−H[10] or L = PR3, R' = Me, H
C2−halogen[11] bond of various neutral azoles to low-valent late
transition metals with formation of complexes bearing pNHC Figure 1. Selected types of NHC and pNHC complexes.
ligands has gained new attention, although this method was first
The oxidative addition of neutral 2-halogenopyridine
derivatives to zero-valent group 10 metal complexes is known as a
[a] Dr. M. C. Jahnke, Dr. R. M. C. Pichl, Prof. Dr. F. E. Hahn* key step in several coupling reactions of halogenopyridine
Institut für Anorganische und Analytische Chemie derivatives with Grignard reagents[18] or in Suzuki-Miyaura
Westfälische Wilhelms-Universität Münster reactions.[19] In addition, the isolation of complexes of type G
Corrensstr. 30, 48149 Münster, Germany
(Figure 1), which possess N-alkylated or N-protonated pyridin-2-
E-mail: fehahn@uni-muenster.de
ylidene ligands (protic-rNHCs)[20] has been described. However,
Supporting information for this article is available on the WWW
under htti://dx.doi.org/10.1002/zaac.2020xxxxx.
1

This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
complexes of type G bearing pyridin-2-ylidene rNHC ligands
could only be prepared following a multistep synthetic protocol via
cleavage of dinuclear species of type H (Figure 1).[20e,21]
We became interested in transferring the direct one-pot
oxidative addition protocol for the preparation of complexes
bearing pNHC ligands from 2-halogenoazoles[3ce,11] to pyridine-
derived aminoheterocycles. In this contribution we describe the
one-pot synthesis of palladium, platinum and nickel complexes
featuring a protic pyridin-2-ylidene or a protic quinolin-2-ylidene
protic-rNHC ligand by the oxidative addition of 2-halogeno-
substituted pyridine-heterocycles to transition metal complexes of
zero-valent d10 metals in the presence of a proton source. This
procedure avoids the dinuclear intermediates of type H (Figure 1).
Results and Discussion
Reaction of a sample of 2-bromopyridine with an equimolar
amount of [Pd(PPh3)4] in the presence of an excess of NH4PF6 as
proton source in toluene at reflux yielded protic-rNHC complex
trans-[1]PF6 (Scheme 1) in a one-pot reaction. Complex trans-
[1]PF6 was isolated after 2 d in moderate yield of 65%. The related
platinum(II) complexes trans-[2]BF4 and trans-[3]BF4 were also
obtained in moderate yields under similar reaction condition from
equimolar amounts of 2-halogenopyridines, [Pt(PPh3)4] and an
excess of NH4BF4 as proton source (Scheme 1). The preparation of
the PtII protic-rNHC complexes with perchlorate counterions has
previously been described.[20a,22] These complexes are included
here since their preparation via the one-pot oxidative addition
procedure is more convenient and additional analytical data and the
molecular structure determinations are now provided.
Scheme 1. Synthesis of palladium and platinum complexes bearing
a protic pyridin-2-ylidene ligand.
The 1H NMR spectrum of trans-[1]PF6 features a broad singlet
at  = 11.75 ppm for the NH proton. The resonance for carbon
atom C2 was observed as a triplet at  = 188.4 ppm (2JCP = 6.8 Hz)
in the 13C{1H} NMR spectrum, clearly indicating the presence of
two chemically identical phosphorous atoms bound to the PdII
center and thus the trans-configuration for the complex cation.
Coupling of the phosphorous atoms to carbon atom C3 was also
observed ((C3) = 136.8 ppm, 3JCP = 3.4 Hz). Triplet resonances
are also observed for the carbon atoms in ipso- ( = 129.8 ppm,
1/3
JCP = 25.2 Hz), ortho- ( = 134.9 ppm, 2/4JCP = 6.3 Hz) and meta-
position ( = 129.1 ppm, 3/5JCP = 5.4 Hz) of the phenyl groups of
the phosphine ligands, while the resonance of the carbon atom in
para-position was recorded as singlet at  = 131.3 ppm. The
31
P{1H} NMR spectrum shows a singlet at  = 22.0 ppm for the
two chemically equivalent phosphine phosphorous atoms. HRMS
spectrometry exhibits the signal with the highest intensity at m/z =
790.0447 (calcd. 790.0465 for C41H35NBrP2Pd, trans-[1]+).
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
The NMR spectra of the two platinum complexes are rather
similar to that of trans-[1]PF6. The NH resonances were found at 
= 12.26 ppm (trans-[2]BF4) and at  = 12.62 ppm (trans-[3]BF4).
Only one resonance was observed for the two PPh3 ligands in the
31
P{1H} NMR spectra at  = 20.9 ppm (trans-[2]BF4, Pt-satellites
1
JPPt = 2690 Hz) and  = 19.2 ppm (trans-[3]BF4, Pt-satellites 1JPPt
= 2672 Hz), indicative for the formation of trans-complex cations.
These values are in good agreement with the values previously
found for the related perchlorate salts.[20a,22] For both complexes,
the C2 carbon atom gave rise to a triplet in the 13C{1H} NMR
spectra at  = 169.1 ppm (2JCP = 8.9 Hz) and  = 170.5 ppm (2JCP =
8.1 Hz). The HRMS mass spectra showed the signals with the
highest intensity at m/z = 834.1582 (calcd. 834.1584 for
C41H35NClP2Pt, trans-[2]+) and m/z = 878.1050 (calcd. 878.1068
Accepted Manuscript
for C41H35NBrP2Pt, trans-[3]+). In accord with previous
observations,[11] complexes trans-[1]PF6trans-[3]BF4 are formed
by an oxidative addition of the C2X bond to the zero-valent metal
center followed by N-protonation. An N-protonation of the 2-
halogenopyridine before the oxidative addition is not possible with
weak acids such as NH4PF6 or NH4BF4.[11a] In addition, no
indications for a C2metal bond cleavage upon N-protonation by
the NH4X salts after the oxidative addition were found.
Crystals of composition trans-[1]PF60.5Et2O, trans-
[2]BF4CH2Cl2 and trans-[3]BF4CH2Cl2 were obtained diffusion
of Et2O into CH2Cl2 solutions of the complexes. The molecular
structures of the three complex cations are depicted in Figure 2.
Figure 2. Molecular structures of trans-[1]+ in trans-
[1]PF6·0.5Et2O (top), trans-[2]+ in trans-[2]BF4·CH2Cl2 (bottom,
left) and trans-[3]+ in trans-[3]BF4·CH2Cl2 (bottom, right)
Displacement ellipsoids are drawn at the 50% probability level.
Hydrogen atoms, except those bound to N1, have been omitted for
clarity. Selected bond lengths /Å and angles /° for trans-[1]+:
PdBr 2.4650(3), PdP1 2.3242(5), PdP2 2.3199(5), PdC1
1.989(2), N1C1 1.352(3), N1C5 1.354(3), C1C2 1.393(3);
BrPdP1 89.116(15), BrPdP2 88.079(15), BrPdC1
177.94(6), P1PdP2 171.32(2), P1PdC1 92.29(6), P2PdC1
90.32(6), C1N1C5 125.0(2), N1C1C2 115.4(2). Selected
bond lengths /Å and angles /° for trans-[2]+ [trans-[3]+]: PtX
2.3732(7) [2.4815(4)], PtP1 2.3210(6) [2.3057(7)], PtP2
2.3044(6) [2.3225(7)], PtC1 1.980(3) [1.987(3)], N1C1 1.356(3)
[1.354(4)], N1C5 1.354(4) [1.348(4)], C1C2 1.395(4)
[1.393(4)]; XPtP1 91.47(2) [88.06(2)], XPtP2 87.76(2)
[91.41(2)], XPtC1 178.31(8) [178.63(8)], P1PtP2 179.21(2)
[179.46(3)], P1PtC1 89.35(7) [91.59(8)], P2PtC1 91.42(7)
[88.93(8)], C1N1C5 124.7(3) [124.7(3)], N1C1C2 115.1(2)
[115.4(3)].
2
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
The complex cations trans-[1]+trans-[3]+ feature a square-
planar coordination geometry with the two PPh3 ligands arranged
in trans-fashion and the pyridin-2-ylidene ligands oriented
perpendicular to the coordination plane. Comparable metric
parameters are rather similar in the three cations. The M‒C1
distances (trans-[1]+ Pd–C1 1.989(2) Å, trans-[2]+ Pt−C1 1.980(3)
Å, trans-[3]+ Pt–C1 1.987(3) Å) and the M−P bond lengths (range
2.3044(6)−2.3242(5) Å) fall in the expected range when compared
to the related complex bearing an N-protonated pyridin-2-ylidene
ligand.[20b] The N1‒C1‒C2 bond angles fall in a narrow range of
115.1(2)115.4(3)° and are significant smaller than the C1‒N1‒C5
bond angles (124.7(3)125.0(2)°). Strong NHF hydrogen bonds
between the complex cation and the BF4 or PF6 anions
(Hseparation about 2.0 Å) were found for compounds trans-
[1]PF6trans-[3]BF4 and all other complexes featuring BF4 or
PF6 counteranions.[11b]
Next, the oxidative addition of 2-halogenated quinoline
derivatives was tested. Similarly to the synthesis of complexes
trans-[1]PF6−trans-[3]BF4 complexes with an N-protonated
quinolin-2-ylidene ligand were obtained by the reaction of
equimolar amounts of 2-chloroquinoline and [M0(PPh3)4] (M = Pd,
Pt) in the presence of NH4BF4 as proton source (Scheme 2). The
PdII complex trans-[4]BF4 and the PtII complex trans-[5]BF4 were
obtained in good yields.
Scheme 2. Oxidative addition of 2-chloroquinoline to [M(PPh3)4]
(M = Pd, Pt).
Characteristic resonances for the NH groups were detected as
broad singulets at  = 12.61 ppm and  = 12.59 ppm in the 1H
NMR spectra of trans-[4]BF4 and trans-[5]BF4, respectively. The
carbene carbon resonances were recorded as triplets (trans-[4]BF4
 = 194.5 ppm, 2JCP = 6.9 Hz; trans-[5]BF4  = 176.9 ppm, 2JCP =
8.5 Hz) in the 13C{1H} NMR spectra, indicating the presence of
two chemically equivalent phosphorous nuclei and thus the trans-
arrangement of the phosphine donors. In addition, only one
resonance was detected for each complex in the 31P{1H} NMR
spectra (trans-[4]BF4  = 22.3 ppm, trans-[5]BF4;  = 20.3 ppm).
The latter resonance also exhibits the characteristic coupling of the
phosphorous atoms with the 195Pt nucleus (Pt-satellites, 1JPPt =
2689 Hz). The HRMS mass spectra show for the PdII complex
trans-[4]BF4 the signal with the highest intensity at m/z = 794.1126
(calcd. 794.1138 for C45H37NClP2Pd, trans-[4]+) and for the PtII
complex trans-[5]BF4 at m/z = 884.1723 (calcd. 884.1742 for
C45H37NClP2Pt, trans-[5]+).
Crystals of trans-[4]BF4CH2Cl2 and trans-[5]BF4CH2Cl2,
suitable for X-ray diffraction studies, were obtained by slow
diffusion of diethyl ether into a saturated solutions of the
complexes in dichloromethane. Both compounds crystallized in the
monoclinic space group P21/c. The molecular structures of the
complex cations trans-[4]+ and trans-[5]+ are depicted in Figure 3.
Both complex cations exhibit the expected square-planar
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
coordination geometry. The quinolin-2-ylidene ligand is oriented
perpendicular to the coordination plane and, similarly to
compounds trans-[1]PF6−trans-[3]BF4, the two PPh3 ligand are
arranged in trans-fashion (P1−M−P2 bond angles: trans-[4]+
174.95(2)°, trans-[5]+ 173.80(3)°). The M−C1 bond length in
trans-[4]+ (1.985(3) Å) and trans-[5]+ (1.981(3) Å) are rather
similar and fall in the range previously described for Pd−CrNHC
(rNHC = N-protonated pyridin-2-ylidene) complexes.[20b] As was
observed for the pyridin-2-ylidene rNHC complexes trans-
[1]PF6trans-[3]BF4, the N1−C1−C2 bond angles in trans-[4]BF4,
and trans-[5]BF4 (116.4(2) and 115.9(3)°) are significantly smaller
than the C1−N1−C9 bond angles (125.5(2) and 125.7(3)°) and fall
in the typical range for complexes bearing pyridin-2-ylidene[20b] or
quinolin-2-ylidene ligands.[23]
Accepted Manuscript
Figure 3. Molecular structures of trans-[4]+ in trans-
[4]BF4·CH2Cl2 (top) and trans-[5]+ in trans-[5]BF4·CH2Cl2
(bottom). Displacement ellipsoids are drawn at the 50% probability
level. Hydrogen atoms, except those bound to N1, have been
omitted for clarity. Selected bond lengths /Å and angles /° for
trans-[4]+ [trans-[5]+]: MCl 2.3536(6) [2.3668(8)], MP1
2.3277(7) [2.3056(9)], MP2 2.3166(7) [2.3126(9)], MC1
1.985(3) [1.981(3)], N1C1 1.331(3) [1.331(4)], N1C9 1.383(3)
[1.382(4)], C1C2 1.420(4) [1.422(5)]; ClMP1 90.53(2)
[86.36(3)], ClMP2 87.09(2) [89.60(3)], ClMC1 177.09(8)
[177.52(10)], P1MP2 174.95(2) [173.80(3)], P1MC1 90.91(7)
[92.46(10)], P2MC1 91.68(7) [91.75(10)], C1N1C9 125.5(2)
[125.7(3)], N1C1C2 116.4(2) [115.9(3)].
The preparation of complex trans-[bis(triethylphosphine)-(NH-
pyridin-2-ylidene)chloridonickel(II)] perchlorate featuring an N-
protonated rNHC ligand derived from pyridine has been
described.[24] The synthesis involved a two-step reaction sequence
starting from 2-chloropyridine and [Ni0(PPh3)4]. In a first
oxidative addition reaction, a dinuclear complex of type H (Figure
1) bearing PPh3 ligands was isolated.[21a,c] Treatment of the
dinuclear complex with PEt3 and HClO4 gave the desired
mononuclear N-protonated protic-rNHC nickel complex.[24] We
have shortened this two-step protocol. Similarly to the previously
described strategy for the preparation of pNHC complexes[11] and
the synthesis of complexes bearing N-protonated rNHC ligands
described above, we performed the oxidative addition of 2-
chloropyridine to Ni0 in the presence of a proton acid and PEt3 as
an auxiliary ligand. Thus [Ni(cod)2] was treated with PEt3 to
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
generate in situ an electron-rich Ni0 complex, which was
subsequently reacted with 2-chloro- or 2-bromopyridine in the
presence of an ammonium salt as proton source. The complexes
trans-[6]BF4 and trans-[7]PF6 were isolated in 59% and 67% yield,
respectively (Scheme 3).
Scheme 3. Synthesis of the nickel rNHC complexes trans-[6]BF4
and trans-[7]PF6.
The characteristic broad signals for the NH groups of trans-
[6]BF4 and trans-[7]PF6 were observed at  = 13.10 ppm and  =
13.41 ppm, respectively. As expected, triplet resonances were
detected for the C2 carbon atoms in the 13C{1H} NMR spectra of
trans-[6]BF4 ( = 193.8 ppm, 2JCP = 33.5 Hz) and trans-[7]PF6 ( =
195.3 ppm, 2JCP = 32.7 Hz). These resonances and the observation
of only one resonance in the 31P{1H} NMR spectra ( = 16.1 ppm
for trans-[6]BF4 and at  = 15.4 ppm for trans-[7]PF6) for the
complex cations confirmed the formation of the trans-complexes.
The 13C{1H} NMR resonances for the PEt3 ligands were recorded
as triplets for the PCH2 groups and as singlets for the terminal CH3
groups. Generally, the NMR spectra of trans-[6]BF4 and trans-
[7]PF6 exhibit only small differences depending on the halogenato
ligand present.
Slow diffusion of diethyl ether into a saturated solution of
trans-[7]PF6 in dichloromethane yielded crystals suitable for an X-
ray diffraction analysis. The molecular structure of complex cation
trans-[7]+ is depicted in Figure 4.
Figure 4. Molecular structure of trans-[7]+ in trans-[7]PF6. Only
one molecule of the three essentially identical molecules in the
asymmetric unit is displayed. Displacement ellipsoids are drawn at
the 50% probability level. Hydrogen atoms, except the one bound
to N1, have been omitted for clarity. Selected bond lengths /Å and
angles /° for trans-[7]: NiBr 2.3297(8), NiP1 2.223(2), NiP2
2.223(2), NiC1 1.849(5), N1C1 1.345(7), N1C5 1.369(8),
C1C2 1.410(8); BrNiP1 88.99(4), BrNiP2 89.89(5),
BrNiC1 179.8(2), P1NiP2 176.87(7), P1NiC1 90.8(2),
P2NiC1 90.4(2), C1N1C5 124.0(6), N1C1C2 115.4(5).
The molecular structure of complex cation trans-[7]+ strongly
resembles those of cations trans-[1]+trans-[3]+ (Figure 2). Major
differences are the shorter NiC1 and NiP bonds caused by the
smaller atomic radius of NiII compared to PdII and PtII. The Ni−C1
bond length in trans-[7]+ (1.849(5) Å) compares well to the
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
equivalent distance in the related NiII complex bearing an N-
alkylated pyridin-2-ylidene ligand.[23] As previously observed for
the related complex cations trans-[1]+trans-[3]+, the N1−C1−C2
bond angle (115.4(5)°) is significantly smaller than the C1−N1−C5
bond angle (124.0(6)°).
Finally, the oxidative addition of 2-chloroquinoline to Ni0 was
investigated in the absence or presence of a proton acid (Scheme 4).
In the absence of a proton acid, we expected the formation of a
complex bearing a remote NHC (rNHC) by oxidative addition of
the CCl bond. In the presence of NH4BF4, formation of the
complex bearing a protic-rNHC ligand is expected. Of course, the
latter complex would also form from the complex bearing an
rNHC ligand obtained from the oxidative addition of 2-
Accepted Manuscript
chloroquinoline to Ni0 and subsequent N-protonation with NH4BF4.
This study aims to show that both the complex with the N-
protonated and the unprotonated quinolin-2-ylidene ligand are
stable enough for isolation.
Initially, 2-chloroquinoline was reacted with [Ni(cod)2] in the
presence of an excess of PEt3 to give the neutral complex trans-[8].
The reaction was then repeated under identical conditions but in
the presence of the proton acid NH4BF4 to yield salt trans-[9]BF4.
N Cl
[Ni(cod) 2], PEt3 [Ni(cod) 2], PEt3
hexane, 25 °C NH4BF4
hexane, 25 °C.
5
4a
4
6 3 BF4
PEt3 PEt3
2
N
7
8a N1
Ni 8 Ni
Cl H Cl
Et3P Et3P
trans-[8] trans-[9]BF4
Scheme 4. Oxidative addition of 2-chloroquinoline to Ni0.
The 1H NMR spectra of trans-[8] and trans-[9]BF4 differ
significantly. While the 1H NMR spectrum of trans-[8] lacks any
resonances downfied from about 8 ppm, the spectrum of trans-
[9]BF4 features a broad resonance at  = 13.50 ppm, which is
characteristic for the NH group of complexes bearing a quinoline-
derived, protic rNHC ligand. In addition, the resonances of the
aromatic protons of the neutral quinolin-2-ylidene ligand in trans-
[9]BF4 are significantly downfield shifted in comparison to the
equivalent resonances of the aromatic protons in trans-[8],
obviously due to the negative charge of the quinolin-2-ylidene
ligand in trans-[8].
Similar observations were made in the 13C{1H} NMR spectra.
The 13C{1H} NMR spectrum of trans-[9]BF4 exhibits a triplet at 
= 204.6 ppm (2JCP = 32.6 Hz) for the C2 carbon atom, significantly
downfield shifted compared the same resonance in trans-[8] at  =
188.7 (2JCP = 33.0 Hz). A downfield shift was also observed for the
phosphorous resonance in the 31P{1H} NMR spectrum of trans-[9]
( = 15.3 ppm) compared to trans-[8]BF4 ( = 11.0 ppm). We
assume, that the general upfield shift of the resonances for trans-
[8] in comparison to trans-[9]BF4 is caused by the negative charge
of the quinolin-2-ylidene ligand in trans-[8]. The HRMS mass
4
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
spectra of the complexes exhibit the highest intensity peaks at m/z
= 458.1439 (calcd. 458.1443 for C21H36NClNiP2, [trans-[8]+H]+)
and m/z = 458.1445 (calcd. 458.1443 for C21H37NClNiP2, trans-
[9]+).
Crystals of trans-[8] and trans-[9]BF4 were obtained by slow
diffusion of diethyl ether into saturated dichloromethane solutions
of the complexes. Both complexes exhibit the expected square-
planar coordination geometry around the nickel atoms with the two
PEt3 ligands arranged in trans fashion. Similarly to the quinolin-2-
ylidene PdII and PtII complexes trans-[4]BF4 and trans-[5]BF4, the
perpendicular orientation of the quinolin-2-ylidene ligand relative
to the coordination plane was also observed for trans-[8] and trans-
[9]BF4. The cationic complex cation trans-[9]+ features metric
parameters which are comparable to those of the NiII pyridine-2-
ylidene complex trans-[7]+.
Figure 5. Molecular structures of trans-[8] (top) and trans-[9]+
(bottom) in trans-[9]BF4. Both complexes reside on
crystallographic mirror planes. Displacement ellipsoids are drawn
at the 50% probability level. Hydrogen atoms, except the one
bound to N1 in trans-[9]+, have been omitted for clarity. Selected
bond lengths /Å and angles /° for trans-[8]+ [trans-[9]+]: NiCl
2.2545(4) [2.1987(6)], NiP1 2.1947(3) [2.2203(4)], NiC1
1.8762(14) [1.846(2)], N1C1 1.323(2) [1.349(3)], N1C9
1.380(2) [1.379(3)], C1C2 1.436(2) [1.435(4)]; ClNiP1
89.739(7) [91.314(13)], ClNiC1 179.08(5) [179.64(8)],
P1NiP1* 177.04(2) [171.65(3)], P1NiC1 90.285(7)
[88.711(14)], C1N1C9 119.09(12) [126.3(2)], N1C1C2
121.26(13) [115.2(2)].
The Ni–C1 bond length in neutral trans-[8] (1.8762(14) Å) is
significantly longer than in cationic trans-[9]+ (1.846(2) Å), while
the Ni‒P bond lengths in complex trans-[8] (2.1947(3) Å) are
significant shorter than in trans-[9]BF4 (2.2203(4) Å). The N-
protonation status of the quinolin-2-ylidene ligand influences the
metric parameters within the aminoheterocycle. The C1N1C9
angle in the deprotonated N-heterocycle in trans-[8] (119.09
(12) °) is smaller than the N1C1C2 angle (121.26(13) °) in
accord with the free electron pair at the ring-nitrogen atom. This
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
situation inverses upon N-protonation in trans-[9]+ where the
C1N1C9 angle becomes significantly larger (126.3(2) °) while
the N1C1C2 angle shrinks to 115.2(2) °. Similar behaviour has
been described for complexes bearing N-deprotonated azolato
ligands and N-protonated pNHC ligands.[25]
Conclusions
We present a versatile one-pot synthesis for the preparation of
complexes bearing protic pyridin-2-ylidene or quinolin-2-ylidene
ligands (protic-rNHC ligands). While PdII and PtII complexes with
a protic pyridin-2-ylidene or quinolin-2-ylidene ligand were
obtained by oxidative addition of 2-halogenopyridine or 2-
chloroqinoline to [M0(PPh3)4] (M = Pd, Pt), the NiII complexes
with these ligands were prepared by treatment of in situ prepared
Accepted Manuscript
[Ni0(PEt3)x] with 2-halogenopyridines or 2-chloroquinolines. The
molecular structure determinations exhibit rather similar bond
angles and distances for comparable metric parameters. Significant
differences in the metric parameters were only observed for
complexes bearing N-deprotonated or N-protonated quinolin-2-
ylidenes.
Experimental Section
All manipulations were carried out under an argon atmosphere
using standard Schlenk or glovebox techniques. Solvents were
dried by standard methods under argon and were freshly distilled
prior to use. 1H, 13C{1H} and 31P{1H} NMR spectra were measured
on a Bruker AVANCE I 400 or a Bruker AVANCE III 400
spectrometer. Chemical shifts () are expressed in ppm using the
residual protonated solvent signal as internal standard. Coupling
constants are expressed in Hertz. Mass spectra were obtained with
an Orbitrap LTQ XL (Thermo Scientific) spectrometer. Ligand
precursors and metal complexes were purchased from commercial
sources and were used without further purification.
Synthesis of trans-[1]PF6: Equimolar amounts of [Pd(PPh3)4]
(0.030 g, 0.026 mmol) and 2-bromopyridine (0.004 g, 0.003 mL,
0.025 mmol) were dissolved in toluene (5 mL) and an excess of
NH4PF4 (0.013 g, 0.08 mmol) was added to this solution. The
reaction mixture was stirred for 2 d at 110 °C. A bright yellow
precipitate formed during this time which was isolated by filtration,
washed with toluene and diethyl ether (10 mL each) and dried in
vacuo. The reaction product was dissolved in dichloromethane (10
mL). The solution was filtered and the solvent was removed from
the filtrate in vacuo to give trans-[1]PF6 as a yellow powder. Yield:
0.016 g (0.017 mmol, 65%). Crystals of trans-[1]PF60.5Et2O were
obtained by slow diffusion of diethyl ether into a saturated solution
of trans-[1]PF6 in dichloromethane. 1H NMR (400 MHz, CD2Cl2,
300 K, ppm):  = 11.75 (s, 1H, NH), 7.77–7.71, (m, 1H, pyridine-
H3), 7.66–7.62 (m, 12H, Ph-Hortho), 7.50–7.48 (m, 1H, pyridine-
H6), 7.46–7.42 (m, 6H, Ph-Hpara), 7.39–7.35 (m, 12H, Ph-Hmeta),
7.06–7.01 (m, 1H, pyridine-H4), 6.70–6.67 (m, 1H, pyridine-H5).
13
C{1H} NMR (100 MHz, CD2Cl2, 300 K, ppm):  = 188.4 (t, 2JCP
= 6.8 Hz, pyridine-C2), 141.9 (pyridine-C6), 138.8 (pyridine-C4),
136.8 (t, 3JCP = 3.4 Hz, pyridine-C3), 134.9 (v-t, 2/4JCP = 6.3 Hz,
Ph-Cortho), 131.3 (Ph-Cpara), 129.8 (v-t, 1/3JCP = 25.2 Hz, Ph-Cipso),
129.1 (v-t, 3/5JCP = 5.4 Hz, Ph-Cmeta), 120.1 (pyridine-C5). 31P{1H}
NMR (162 MHz, CD2Cl2, 300 K, ppm):  = 22.0 (s), –144.1 (sept,
1
JPF = 713.6 Hz). HRMS (ESI, positive ions): m/z = 790.0447
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
(calcd. 790.0465 for C41H35NBrP2Pd, trans-[1]+), 708.1197 (calcd.
708.1217 for C41H34NP2Pd, {trans-[1] ‒ HBr}+). IR (KBr, cm–1): ṽ
= 3261 (NH).
Synthesis of trans-[2]BF4: An equimolar amount of [Pt(PPh3)4]
(0.032 g, 0.026 mmol) and 2-chloropyridine (0.003 g, 0.003 mL,
0.026 mmol) was mixed together with an excess of NH4BF4 (0.008
g, 0.076 mmol) in toluene (5 mL). The reaction mixture was heated
under reflux for 4 d. Over this period a precipitate formed. The
precipitate was separated by filtration, washed with toluene and
diethyl ether (10 mL each) and dried in vacuo. The residue was
then dissolved in dichloromethane (10 mL) and mixture was
filtered. The solvent from the filtrate was removed in vacuo to give
trans-[2]BF4 as a bright yellow solid. Yield: 0.012 g (0.013 mmol,
50%). Crystals of trans-[2]BF4CH2Cl2 were obtained by slow
diffusion of diethyl ether into a saturated dichloromethane solution
of trans-[2]BF4. 1H NMR (400 MHz, CD2Cl2, 300 K, ppm):  =
12.26 (s, 1H, NH), 7.69–7.64 (m, 12H, Ph-Hortho), 7.47–7.42 (m,
6H, Ph-Hpara), 7.40–7.37 (m, 12H, Ph-Hmeta), 7.24–7.19 (m, 1H,
pyridine-H3), 7.06–7.05 (m, 1H, pyridine-H6), 6.93–6.89 (m, 1H,
pyridine-H4), 6.58–6.55 (m, 1H, pyridine-H5). 13C{1H} NMR (100
MHz, CD2Cl2, 300 K, ppm):  = 169.1 (t, 2JCP = 8.9 Hz, pyridine-
C2), 141.3 (pyridine-C6), 139.1 (pyridine-C4), 138.1 (pyridine-C3),
134.9 (v-t, 2/4JCP = 6.2 Hz, Ph-Cortho), 131.4 (Ph-Cpara), 129.1 (v-t,
3/5
JCP = 5.5 Hz, Ph-Cmeta), 128.5 (v-t, 1/3JCP = 29.3 Hz, Ph-Cipso),
119.2 (pyridine-C5). 31P{1H} NMR (162 MHz, CD2Cl2, 300 K,
ppm):  = 20.9 (s, Pt-satellites 1JPPt = 2690 Hz). HRMS (ESI,
positive ions): m/z = 834.1582 (calcd. 834.1584 for C41H35NClP2Pt,
trans-[2]+). IR (KBr, cm–1): ṽ = 3240 (NH).
Synthesis of trans-[3]BF4: [Pt(PPh3)4] (0.032 g, 0.026 mmol), 2-
bromopyridine (0.004 g, 0.003 ml, 0.025 mmol) and NH4BF4
(0.008 g, 0.076 mmol) were dissolved in toluene (5 mL). The
reaction mixture was heated at 110 °C for 2 d. During this time a
precipitate formed which was by filtration, washed with toluene
and diethyl ether (10 mL each) and dried in vacuo. The white
residue was then dissolved in dichloromethane (10 mL) and the
mixture was filtered. Removal of the solvent from the filtrate in
vacuo yielded trans-[3]BF4. Yield: 0.013 g (0.013 mmol, 50%).
Crystals of trans-[3]BF4CH2Cl2 were obtained by slow diffusion
of diethyl ether into a saturated dichloromethane solution of trans-
[3]BF4. 1H NMR (400 MHz, CD2Cl2/DMSO-d6, 300 K, ppm):  =
12.62 (s, 1H, NH), 7.66–7.64 (m, 12H, Ph-Hortho), 7.46–7.42 (m,
6H, Ph-Hpara), 7.39–7.32 (m, 12H, Ph-Hmeta), 7.237.12 (m, 2H,
pyridine-H3, -H6), 6.94–6.90 (m, 1H, pyridine-H4), 6.61–6.58 (m,
1H, pyridine-H5). 13C{1H} NMR (100 MHz, CD2Cl2/DMSO-d6,
300 K, ppm):  = 170.5 (t, 2JCP = 8.1 Hz, pyridine-C2), 141.2
(pyridine-C6), 139.2 (pyridine-C4), 137.7 (pyridine-C3), 135.0 (v-t,
2/4
JCP = 6.4 Hz, Ph-Cortho), 131.4 (Ph-Cpara), 128.9 (v-t, 3/5JCP = 5.4
Hz, Ph-Cmeta), 128.4 (Ph-Cipso), 119.3 (pyridine-C5). 31P{1H} NMR
(162 MHz, CD2Cl2/DMSO-d6, 300 K, ppm):  = 19.2 (s, Pt-
satellites 1JPPt = 2672 Hz). HRMS (ESI, positive ions): m/z =
878.1050 (calcd. 878.1068 for C41H35NBrP2Pt, trans-[3]+). IR
(KBr, cm–1): ṽ = 3313 (NH).
Synthesis of trans-[4]BF4: Equimolar amounts of [Pd(PPh3)4]
(0.030 g, 0.026 mmol) and 2-chloroquinoline (0.004 g, 0.024
mmol) were dissolved in toluene (5 mL) and an excess of NH4BF4
(0.008 g, 0.076 mmol) was added to the solution. The reaction
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
mixture was stirred for 2 d at 120 °C. During this period a
precipitate formed which was isolated by filtration, washed with
toluene and diethyl ether (10 mL each) and dried in vacuo. The
solid was then dissolved in dichloromethane (10 mL). The solution
was filtered and the solvent was removed from the filtrate in vacuo
to give trans-[4]BF4 as colorless solid. Yield: 0.016 g (0.018 mmol,
69%). Crystals of trans-[4]BF4CH2Cl2 were obtained by slow
diffusion of diethyl ether into a saturated dichloromethane solution
of trans-[4]BF4. 1H NMR (400 MHz, CD2Cl2, 300 K, ppm):  =
12.61 (s, 1H, NH), 7.73–7.68 (m, 12H, Ph-Hortho), 7.63–7.53 (m,
4H, quin-H), 7.50–7.41 (m, 2H, quin-H), 7.27–7.26 (m, 18H, Ph-
Hmeta, Ph-Hpara). 13C{1H} NMR (100 MHz, CD2Cl2, 300 K, ppm):
 = 194.5 (t, 2JCP = 6.9 Hz, quin-C2), 140.2 (quin-C8a), 137.3
(quin-C4), 134.8 (v-t, 2/4JCP = 6.4 Hz, Ph-Cortho), 132.2 (quin-C7),
Accepted Manuscript
131.2 (Ph-Cpara), 130.9 (quin-C3), 129.2 (v-t, 1/3JCP = 24.9 Hz, Ph-
Cipso), 128.8 (v-t, 3/5JCP = 5.4 Hz, Ph-Cmeta), 128.0 (quin-C5), 127.8
(quin-C6), 124.9 (quin-C4a), 120.0 (quin-C8). 31P{1H} NMR (162
MHz, CD2Cl2, 300 K, ppm):  = 22.3 (s). HRMS (ESI, positive
ions): m/z = 794.1126 (calcd. 794.1138 for C45H37NClP2Pd, trans-
[4]+).
Synthesis of trans-[5]BF4: The synthesis of compound trans-
[5]BF4 was achieved as described for the preparation of trans-
[4]BF4 from 2-chloroquinoline (0.004 g, 0.024 mmol) and
[Pt(PPh3)4] (0.032 g, 0.026 mmol) in the presence of NH4BF4
(0.008 g, 0.076 mmol). Yield: 0.013 g (0.013 mmol, 50%).
Crystals of trans-[5]BF4CH2Cl2 were obtained by slow diffusion
of diethyl ether into a saturated dichloromethane solution of trans-
[5]BF4. 1H NMR (400 MHz, CD2Cl2, 300 K, ppm):  = 12.59 (s,
1H, NH), 7.74–7.70 (m, 12H, Ph-Hortho), 7.67–7.31 (m, 6H, quin-
H), 7.28–7.20 (m, 18H, Ph-Hmeta, Ph-Hpara). 13C{1H} NMR (100
MHz, CD2Cl2, 300 K, ppm):  = 176.9 (t, 2JCP = 8.5 Hz, quin-C2),
139.9 (quin-C8a), 137.9 (quin-C4), 134.9 (v-t, 2/4JCP = 6.2 Hz, Ph-
Cortho), 132.0 (quin-C7), 131.8 (quin-C3), 131.3 (Ph-Cpara), 128.8
(v-t, 3/5JCP = 5.5 Hz, Ph-Cmeta), 128.4 (v-t, 1/3JCP = 29.3 Hz, Ph-
Cipso), 127.62 (quin-C5), 127.58 (quin-C6), 124.7 (quin-C4a),
119.8 (quin-C8). 31P{1H} NMR (162 MHz, CD2Cl2, 300 K, ppm):
 = 20.3 (s, Pt-satellites, 1JPPt = 2689 Hz). HRMS (ESI, positive
ions): m/z = 884.1723 (calcd. 884.1742 for C45H37NClP2Pt, trans-
[5]+). IR (KBr, cm–1): ṽ = 3336 (NH).
Synthesis of trans-[6]BF4: [Ni(cod)2] (0.030 g, 0.109 mmol) was
dissolved in hexane (5 mL) and PEt3 (0.064 g, 0.080 mL, 0.542
mmol) was added. The color of the mixture instantaneously turned
from yellow to red. After 15 minutes of stirring, 2-chloropyridine
(0.013 g, 0.010 mL, 0.114 mmol) and an excess of NH4BF4 (0.035
g, 0.334 mmol) were added and the reaction mixture was stirred for
12 h at ambient temperature. The obtained orange precipitate
formed over this period was isolated by filtration and washed with
hexane and diethyl ether (10 mL each). The solid residue was
dissolved in dichloromethane (10 mL). The solution was filtered
and the solvent was removed in vacuo from the filtrate to give
trans-[6]BF4 as a bright yellow solid. Yield: 0.032 g (0.064 mmol,
59%). Crystals of trans-[6]BF4 were obtained by slow diffusion of
diethyl ether into a saturated dichloromethane solution of trans-
[6]BF4. 1H NMR (400 MHz, CD2Cl2, 300 K, ppm):  = 13.10 (s,
1H, NH), 8.57–8.50 (m, 1H, pyridine-H6), 8.07 (d, 3J = 8.5 Hz, 1H,
pyridine-H3), 7.53 (t, 3J = 7.5 Hz, 1H, pyridine-H4), 7.17–7.10 (m,
1H, pyridine-H5), 1.65–1.33 (m, 12H, PCH2CH3), 1.22–1.14 (m,
6
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
18H, PCH2CH3). 13C{1H} NMR (100 MHz, CD2Cl2, 300 K, ppm):
 = 193.8 (t, 2JCP = 33.5 Hz, pyridine-C2), 143.3 (pyridine-C6),
137.3 (pyridine-C3), 136.4 (pyridine-C4), 119.5 (pyridine-C5),
14.5 (v-t, 1/3JCP = 13.6 Hz, PCH2CH3), 8.2 (PCH2CH3). 31P{1H}
NMR (162 MHz, CD2Cl2, 300 K, ppm):  = 16.1 (s). HRMS (ESI,
positive Ions): m/z = 408.1288 (calcd. 408.1267 for
C17H35NClNiP2, trans-[6]+).
Synthesis of trans-[7]PF6: Complex trans-[7]PF6 was prepared as
described for trans-[6]BF4 from [Ni(cod)2] (0.030 g, 0.109 mmol),
PEt3 (0.064 g, 0.080 mL, 0.542 mmol), 2-bromopyridine (0.017 g,
0.010 mL, 0.108 mmol) and NH4PF6 (0.054 g, 0.331 mmol). Yield:
0.044 g (0.073 mmol, 67%) of a yellow-orange solid. Crystals of
trans-[7]PF6 were obtained by slow diffusion of diethyl ether into a
saturated dichloromethane solution of the complex. 1H NMR (400
MHz, CD2Cl2, 300 K, ppm):  = 13.41 (s, 1H, NH), 8.54–8.34 (m,
1H, pyridine-H6), 8.15–7.97 (m, 1H, pyridine-H3), 7.69–7.52 (m,
1H, pyridine-H4), 7.28–7.11 (m, 1H, pyridine-H5), 1.76–1.37 (m,
12H, PCH2CH3), 1.35–0.99 (m, 18H, PCH2CH3). 13C{1H} NMR
(100 MHz, CD2Cl2, 300 K, ppm):  = 195.3 (t, 2JCP = 32.7 Hz,
pyridine-C2), 142.8 (pyridine-C6), 137.4 (pyridine-C3), 136.8
(pyridine-C4), 119.8 (pyridine-C5), 15.3 (v-t, 1/3JCP = 13.9 Hz,
PCH2CH3), 8.3 (PCH2CH3). 31P{1H} NMR (162 MHz, CD2Cl2,
300 K, ppm):  = 15.4 (s), –144.2 (sept, 1JPF = 714.2 Hz). HRMS
(ESI, positive Ions): m/z = 454.0753 (calcd. 454.0755 for
C17H35NBrNiP2, trans-[7]+), 408.1289 (calcd. 408.1287 for
C17H35NClNiP2, [trans-[7]‒Br+Cl]+).
Synthesis of trans-[8]: A solution of [Ni(cod)2] (0.030 g, 0.109
mmol) in hexane (5 mL) was treated with PEt3 (0.064 g, 0.080 mL,
0.542 mmol). After 15 min the obtained red solution was treated
with 2-chloroquinoline (0.018 g, 0.110 mmol) and the reaction
mixture was stirred for 12 h at ambient temperature. A color
change from red to yellow was observed. Removal of the solvent in
vacuo yielded trans-[8] as yellow greenish solid. Crystals of trans-
[8]BF4 were obtained by slow diffusion of diethyl ether into a
saturated dichloromethane solution of the complex. Yield: (0.038 g,
0.083 mmol, 76%). 1H NMR (400 MHz, CD2Cl2, 300 K, ppm):  =
7.877.80 (m, 1H, quin-H8), 7.627.48 (m, 3H, quin-H3, -H5, -
H7), 7.347.23 (m, 2H, quin-H4, -H6), 1.42–1.23 (m, 12H,
PCH2CH3), 1.17–1.10 (m, 18H, PCH2CH3). 13C{1H} NMR (100
MHz, CD2Cl2, 300 K, ppm):  = 188.7 (t, 2JCP = 33.0 Hz, quin-C2),
148.5 (quin-C8a), 130.6 (t, 3JCP = 4.0 Hz, quin-C3), 128.3 (quin-C7,
-C8), 128.2 (quin-C4, -C5), 125.1 (quin-C4a), 123.8 (quin-C6),
14.0 (v-t, 1/3JCP = 12.2 Hz, PCH2CH3), 8.2 (PCH2CH3). 31P{1H}
NMR (162 MHz, CD2Cl2, 300 K, ppm):  = 11.0 (s). HRMS (ESI,
positive ions): m/z = 458.1439 (calcd. 458.1443 for C21H37NClNiP2,
[trans-[8]+H]+).
Synthesis of trans-[9]BF4: A sample of [Ni(cod)2] (0.030 g, 0.109
mmol) was dissolved in hexane (5 mL) and PEt3 (0.064 g, 0.080
mL, 0.542 mmol) was added. The color of the reaction mixture
turned instantaneously from yellow to red. After stirring for 15
minutes 2-chloroquinoline (0.018 g, 0.110 mmol) and NH4BF4
(0.035 g, 0.334 mmol) were added and the reaction mixture was
stirred for 24 h at ambient temperature. The formed green
precipitate was isolated by filtration and washed with hexane and
diethyl ether (10 mL each). The solid was then dissolved in
dichloromethane (10 mL) and the solution was filtered. Removal of
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
the solvent from the filtrate in vacuo yielded trans-[9]BF4 as a
greed solid. Yellow-green crystals of trans-[9]BF4 were obtained
by slow diffusion of diethyl ether into a saturated dichloromethane
solution of trans-[9]BF4. Yield: 0.038 g (0.070 mmol, 64%). 1H
NMR (400 MHz, CD2Cl2, 300 K, ppm):  = 13.50 (s, 1H, NH),
8.41 (d, 3J = 7.5 Hz, 1H, quin-H8), 8.21 (d, 3J = 7.9 Hz, 1H, quin-
H3), 7.93–7.85 (m, 3H, quin-H4, -H5, -H7), 7.68–7.60 (m, 1H,
quin-H6), 1.66–1.39 (m, 12H, PCH2CH3), 1.22–1.12 (m, 18H,
PCH2CH3). 13C{1H} NMR (100 MHz, CD2Cl2, 300 K, ppm):  =
204.6 (t, 2JCP = 32.6 Hz, quin-C2), 141.7 (quin-C8a), 134.1 (quin-
C4), 133.2 (quin-C7), 131.5 (quin-C3), 129.0 (quin-C5), 128.1
(quin-C6), 125.0 (quin-C4a), 119.5 (quin-C8), 14.8 (v-t, 1/3JCP =
13.5 Hz, PCH2CH3), 8.3 (PCH2CH3). 31P{1H} NMR (162 MHz,
CD2Cl2, 300 K, ppm):  = 15.3 (s). HRMS (ESI, positive ions):
Accepted Manuscript
m/z = 458.1445 (calcd. 458.1443 for C21H37NClNiP2, trans-[9]+).
IR (KBr, cm–1): ṽ = 3333 (NH).
X-ray Crystallography: Suitable crystals were mounted on a
Bruker APEX-II CCD diffractometer equipped with a microsource
using monochromated MoKα radiation ( = 0.71073 Å). All
diffraction data were collected at 153(2) K. The data reductions
were performed with the Bruker SAINT program package. Structure
solutions were found with the SHELXT[26] package using direct
methods and structure solutions were refined with SHELXL[27]
against F2of all intensities using first isotropic and later
anisotropic thermal parameters for all non-hydrogen atoms.
Hydrogen atoms were added to the structure models in calculated
positions.
Crystallographic data (including structure factors) for the structures
in this paper have been deposited with the Cambridge
Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge
CB21EZ, UK. Copies of the data can be obtained free of charge on
quoting the depository numbers CCDC-2018239 (trans-
[1]PF60.5Et2O), CCDC-2018243 (trans-[2]BF4CH2Cl2), CCDC-
2018240 (trans-[3]BF4CH2Cl2), CCDC-2018244 (trans-
[4]BF4CH2Cl2), CCDC-2018241 (trans-[5]BF4CH2Cl2), CCDC-
2018245 (trans-[7]PF6), CCDC-2018246 (trans-[8]), CCDC-
2018242 (trans-[9]BF4) (Fax: +44-1223-336033; E-mail:
deposit@ccdc.cam.ac.uk, http/www.ccdc.cam.ac.uk).
Supporting information: NMR spectra of all complexes and
selected crystallographic details of compounds trans-
[1]PF6Et2O‒trans-[5]BF4CH2Cl2 and trans-[7]PF6‒trans-[9]BF4.
Acknowledgements
Financial support by the Deutsche Forschungsgemeinschaft (SFB
858 and IRTG 2027) is gratefully acknowledged.
Keywords: Remote Carbenes • Oxidative Addition • Palladium •
Platinum • Nickel
References
[1] a) M. C. Jahnke, F. E. Hahn, Coord. Chem. Rev. 2015,
293‒294, 95‒115; b) M. C. Jahnke, F. E. Hahn, Chem. Lett.
2015, 44, 226‒237; c) S. Kuwata, F. E. Hahn, Chem. Rev.
2018, 118, 9642‒9677.
[2] a) F. E. Hahn, M. C. Jahnke, Angew. Chem. Int. Ed. 2008, 47,
3122‒3172; b) M. C. Jahnke, F. E. Hahn, Top. Organomet.
7
Zeitschrift für anorganische und allgemeine Chemie
ARTICLE
Chem. 2010, 30, 95‒129; c) M. N. Hopkinson, C. Richter, M.
Schedler, F. Glorius, Nature 2014, 510, 485‒496.
[3] a) F. E. Hahn, V. Langenhahn, T. Pape, Chem. Commun.
2005, 5390‒5392; b) P. G. Edwards, F. E. Hahn, Dalton
Trans. 2011, 40, 10278‒10288; c) T. Kösterke, J. Kösters,
E.-U. Würthwein, C. Mück-Lichtenfeld, C. Schulte to Brinke,
F. Lahoz, F. E. Hahn, Chem. Eur. J. 2012, 18, 14594‒14598;
d) R. Das, C. G. Daniliuc, F. E. Hahn, Angew. Chem. Int. Ed.
2014, 53, 1163‒1166; e) R. Das, A. Hepp, C. G. Daniliuc, F.
E. Hahn, Organometallics 2014, 33, 6975‒6987.
[4] a) N. Meier, F. E. Hahn, T. Pape, C. Siering, S. R. Waldvogel,
Eur. J. Inorg. Chem. 2007, 1210‒1214; b) S. Kuwata, T.
Ikariya, Chem. Eur. J. 2011, 17, 3542‒3556; c) S. Kuwata, T.
Ikariya, Chem. Commun. 2014, 50, 14290‒14300; d) F. E.
Hahn, ChemCatChem 2013, 5, 419‒430.
[5] a) V. Miranda-Soto, D. B. Grotjahn, A. G. DiPasquale, A. L.
Rheingold, J. Am. Chem. Soc. 2008, 130, 13200‒13201; b) V.
Miranda-Soto, D. B. Grotjahn, A. L. Cooksy, J. A. Golen, C.
E. Moore, A. L. Rheingold, Angew. Chem. Int. Ed. 2011, 50,
631‒635; c) S. Cepa, C. Schulte to Brinke, F. Roelfes, F. E.
Hahn, Organometallics 2015, 34, 5454‒5460; d) H. Jin, C.
Mück-Lichtenfeld, A. Hepp, D. W. Stephan, F. E. Hahn,
Chem. Eur. J., 2017, 23, 5943‒5947.
[6] a) F. E. Hahn, V. Langenhahn, N. Meier, T. Lügger, W. P.
Fehlhammer, Chem. Eur. J. 2003, 9, 704‒712; b) F. E. Hahn,
C. Garciá Plumed, M. Münder, T. Lügger, Chem. Eur. J.
2004, 10, 6285‒6293.
[7] a ) J. Ruiz, B. F. Perandones, J. Am. Chem. Soc. 2007, 129,
9298‒9299; b) M. A. Huertos, J. Pérez, L. Riera, J. Díaz, R.
López, Angew. Chem. Int. Ed. 2010, 49, 6409‒6412; c) J.
Ruiz, D. Sol, J. F. Van der Maelen, M. Vivanco,
Organometallics 2017, 36, 1035‒1041.
[8] H. G. Raubenheimer, L. Lindeque, S. Cronje, J. Organomet.
Chem. 1996, 511, 177‒184.
[9] a) X. Wang, H. Chen, X. Li, Organometallics 2007, 26,
4684‒4687; b) M. C. Jahnke, D. Brackemeyer, T. Pape, F. E.
Hahn, Heteroatom Chem. 2011, 22, 476‒490; c) G. E.
Dobereiner, C. A. Chamberlin, N. D. Schley, R. H. Crabtree,
Organometallics 2010, 29, 5728‒5731.
[10] K. L. Tan, R. G. Bergman, J. A. Ellman, J. Am. Chem. Soc.
2002, 124, 3202‒3203.
[11] a) T. Kösterke, T. Pape, F. E. Hahn, J. Am. Chem. Soc. 2011,
133, 2112‒2115; b) T. Kösterke, T. Pape, F. E. Hahn, Chem.
Commun. 2011, 47, 10773‒10775.
[12] a) P. J. Fraser, W. R. Roper, F. G. A. Stone, J. Organomet.
Chem. 1973, 50, C54‒C56; b) P. J. Fraser, W. R. Roper, F. G.
A. Stone, J. Chem. Soc. Dalton Trans. 1974, 102‒105.
[13] a) K. Araki, S. Kuwata, T. Ikariya, Organometallics 2008, 27,
2176‒2178; b) F. E. Hahn, A. R. Naziruddin, A. Hepp, T.
Pape, Organometallics 2010, 29, 5283‒5288; c) A. R.
Naziruddin, A. Hepp, T. Pape, F. E. Hahn, Organometallics
2011, 30, 5859‒5866; d) D. Brackemeyer, C. Schulte to
This article is protected by copyright. All rights reserved.
10.1002/zaac.202000279
Brinke, F. Roelfes, F. E. Hahn, Dalton Trans. 2017, 46,
4510‒4513.
[14] a) K. J. Cavell, D. S.McGuinness, Coord. Chem. Rev. 2004,
248, 671‒681; b) A. Fürstner, G. Seidel, D. Kremzow, C. W.
Lehmann, Organometallics 2003, 22, 907‒909.
[15] a) R. M. C. Branzan, J. Kösters, M. C. Jahnke, F. E. Hahn, Z.
Naturforsch. 2016, 71b, 1077‒1085; b) A. Hervé, M. C.
Jahnke, T. Pape, F. E. Hahn, Z. Anorg. Allg. Chem. 2013, 639,
2450‒2454.
[16] H. Jin, T. T. Y. Tan, F. E. Hahn, Angew. Chem. Int. Ed. 2015,
54, 13811‒13815.
[17] a) D. Brackemeyer, A. Hervé, C. Schulte to Brinke, M. C.
Jahnke, F. E. Hahn, J. Am. Chem. Soc. 2014, 136,
7841‒7844; b) F. Kampert, D. Brackemeyer, T. T. Y. Tan, F.
E. Hahn, Organometallics 2018, 37, 4181‒4185.
Accepted Manuscript
[18] K. Tamao, S.-i. Kodama, T. Nakatsuka, Y. Kiso, M. Kumada,
J. Am. Chem. Soc. 1975, 97, 4405‒4406.
[19] a) C. Sicre, A. A. C. Braga, F. Maseras, M. M. Cid,
Tetrahedron 2008, 64, 7437‒7443; b) C. Sicre, J.-L. Alonso-
Gómez, M. M. Cid, Tetrahedron 2006, 62, 11063‒11072; c)
A. Beeby, S. Bettington, I. J. S. Fairlamb, A. E. Goeta, A. R.
Kapdi, E. H. Niemelӓ, A. L. Thompson, New J. Chem. 2004,
28, 600‒605.
[20] a) B. Crociani, F. Di Bianca, A. Giovenco, A. Scrivanti, J.
Organomet. Chem. 1983, 251, 393‒411; b) F. Benetollo, G.
Bombieri, F. DiBianca, B. Crociani, Inorg. Chim. Acta 1991,
188, 51‒53; c) H. G. Raubenheimer, J. G. Toerien, G. J.
Kruger, R. Otte, W. van Zyl, P. Olivier, J. Organomet. Chem.
1994, 446, 291‒295; d) A. Poulain, A. Neels, M. Albrecht,
Eur. J. Inorg. Chem. 2009, 1871‒1881; e) O. Schuster, L.
Yang, H. G. Raubenheimer, M. Albrecht, Chem. Rev. 2009,
109, 3445‒3478.
[21] a) K. Isobe, Y. Nakamura, S. Kawaguchi, Chem. Lett. 1977,
1383‒1386; b) K. Isobe, E. Kai, Y. Nakamura, K. Nishimoto,
T. Miwa, S. Kawaguchi, K. Kinoshita, K. Nakatsu, J. Am.
Chem. Soc. 1980, 102, 2475‒2476; c) K. Isobe, Y. Nakamura,
S. Kawaguchi, Bull. Chem. Soc. Jpn. 1980, 53, 139‒145; d)
K. Isobe, Y. Nakamura, T. Miwa, S. Kawaguchi, Bull. Chem.
Soc. Jpn. 1987, 60, 149‒157.
[22] B. Crociani, F. Di Bianca. A. Giovenco, A. Berton, R.
Bertani, J. Organomet. Chem. 1989, 361, 255‒267.
[23] S. K. Schneider, G. R. Julius, C. Loschen, H. G.
Raubenheimer, G. Frenking, W. A. Herrmann, Dalton Trans.
2006, 1226‒1233.
[24] B. Crociani, F. Di Bianca, A. Giovenco, A. Berton, J.
Organomet. Chem. 1987, 323, 123‒134.
[25] J. Blumenberg, L. B. F. Wilm, F. E. Hahn, Organometallics
2020, 39, 1281‒1287.
[26] G. M. Sheldrick, Acta Cryst. 2015, A71, 3–8.
[27] G. M. Sheldrick, Acta Cryst. 2015, C71, 3–8.
Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000279

ARTICLE
Entry for the Table of Contents

FULL PAPER
M. C. Jahnke, R. M. C. Branzan, F. E.
Hahn*

Page No. – Page No.

Oxidative Addition of 2-Halogeno-

pyridines and 2-Chloroquinoline to
Zero-Valent Group 10 Metals

Accepted Manuscript
Complexes bearing protic rNHC ligands have been prepared by oxidative addition
of 2-halogenopyridines or 2-chloroquinoline to zero-valent group 10 metal
complexes in the presence of a proton acid. In the absence of the acid, the NiII
complex bearing an anionic rNHC ligand has been obtained.

This article is protected by copyright. All rights reserved.

Zeitschrift für anorganische und allgemeine Chemie 10.1002/zaac.202000279

ARTICLE
Additional Author information for the electronic version of the article.
Author: F. E. Hahn Orchid 0000-0002-2807-7232

Accepted Manuscript

10

This article is protected by copyright. All rights reserved.