Early-Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

Article abstract of DOI:10.1002/chem.201600476

OH functionalized triarylphosphines were used to assemble zirconocene-based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early-late heterometallic compou

Full text of DOI:10.1002/chem.201600476

DOI: 10.1002/chem.201600476
Full Paper
&
Inorganic Chemistry
Early–Late Heterometallic Complexes of Gold and Zirconium:
Photoluminescence and Reactivity
Sebastian Bestgen,[a] Christoph Schoo,[a] Christina Zovko,[a] Ralf Kçppe,[a] Rory P. Kelly,[a]
Sergei Lebedkin,[b] Manfred M. Kappes,[b] and Peter W. Roesky*[a]
Abstract: OH functionalized triarylphosphines were used to
assemble zirconocene-based metalloligands with phosphine
donor sites in varying positions. These complexes were sub-
sequently treated with different gold precursors to obtain
early–late heterometallic compounds in which the metal
atoms exhibit different intermetallic distances. All com-
pounds were fully investigated by spectroscopic techniques,
photoluminescence measurements and single crystal X-ray
diffraction. Quantum chemical calculations were also per-
formed. Some compounds show bright emission even at
room temperature with quantum yields of up to 19% (exci-
tation at 350 nm). Furthermore, the reactivity of dimethyl zir-
conocene derivatives towards gold complexes was investi-
gated, revealing simultaneous ligand exchange and transme-
tallation reactions.
Introduction
plications in catalysis, oxide materials like TiO2 or ZrO2 are suit-
able support materials for the anchoring of organic molecules.
Besides bulk samples, the supports can consist of thin layers or
nanoparticles. Biologically relevant molecules or organometal-
lic compounds can then be bound to the surface-attached an-
choring groups, leading to surface-functionalized materials
that can be used as phosphors or catalysts.[8–10] Hence, the as-
sembly of two electronically different metals within one com-
plex can act as a model system to investigate intermetallic
communication or cooperative behaviour with respect to their
luminescent or catalytic properties.[2]
The combination of early and late transition metals within one
organometallic compound to afford early–late heterobimetallic
complexes (ELHBs) has been extensively investigated over the
past few decades.[1] Interest in these complexes is driven by
their potential use in heterobimetallic catalysis. Central aims in-
clude the development of more active catalysts, the investiga-
tion of novel catalytic transformations, and the catalysis of two
different reactions in one system.[2,3] Moreover, the investiga-
tion of ELHBs contributes to a better understanding of inter-
metallic interactions, as can be found in bioinorganic sys-
tems,[4] and solid-state compounds, including luminescent ma-
terials and heterogeneous catalysts.[5,6] In these materials,
a late precious metal (e.g., Pd or Pt) is attached to an oxide
surface (support) like MgO or Al2O3. Higher catalytic activity is
often achieved compared to the bulk metal, and this can be
attributed to interactions between the precious metal and the
support. This can be understood as electronic communication
between the early and late transition metals and/or coopera-
tive activation of the substrates.[7] In addition to potential ap-
The synthesis of heterometallic ELHBs usually requires ligand
systems which take the different affinities of the metals for cer-
tain donor atoms into account. Typically, soft donor centres
(phosphines, NHCs or thiolates) are combined with hard donor
centres (alkoxides, amidinates) on a common backbone.[11–14]
Another possibility is the synthesis of a mono- or polynuclear
complex which can function as a metalloligand for the coordi-
nation of other metals.[6,15–20] This approach could also be used
to synthesize ELHBs of gold and zirconium and this particular
combination of metals is attractive with regard to the photo-
physical properties of the resulting complexes. Gold(I) com-
pounds often display interesting photoluminescence (PL) be-
haviour,[21–25] which can be significantly influenced by interme-
tallic interactions[12] in polynuclear gold compounds.[26] Zirconi-
um complexes, in particular zirconocene-based ones, also
often show intense PL in the visible range.[27–29] It can be ex-
pected that the electronic communication between the metal
sites would directly influence the photophysical properties of
the Au–Zr compounds. Furthermore, structurally characterized
ELHBs of gold and zirconium are scarce. A search of the Cam-
bridge Structural Database revealed that only six heterometal-
lic compounds of these metals are known.[5,6,30] Herein, we
present the synthesis of zirconocene-based metalloligands as
[a] S. Bestgen, C. Schoo, C. Zovko, Dr. R. Kçppe, Dr. R. P. Kelly,
Prof. Dr. P. W. Roesky
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT)
Engesserstraße 15, 76131 Karlsruhe (Germany)
E-mail: roesky@kit.edu
[b] Dr. S. Lebedkin, Prof. Dr. M. M. Kappes
Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT)
Fritz-Haber Weg 2, 76131 Karlsruhe (Germany)
and
Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT)
Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen
(Germany)
Supporting information for this article can be found under http://
dx.doi.org/10.1002/chem.201600476.
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1
model compounds for zirconium-oxide-anchored ligands and
give a full account of their AuI chemistry. The reactivity of
methyl-substituted zirconocenes with gold substrates, as well
as their photoluminescence properties are discussed. The role
of metal–metal bonding is discussed by means of quantum-
chemical calculations. Investigation of polynuclear Au–Zr
based ELHBs, with respect to their photophysical properties,
has not been described in the literature to date.
cally equivalent, showing a singlet at 5.89 ppm in the H NMR
spectrum. In the 13C{1H} NMR spectrum, the phenolic C-atom is
shifted downfield to 166.9 ppm. Both phosphorus atoms ex-
hibit a chemical shift of À6.6 ppm in the 31P{1H} NMR spec-
trum, and this is in the usual region for unsaturated triaryl-
phosphines. The metalloligand 1 was also characterized by
single-crystal X-ray diffraction. It crystallizes in the orthorhom-
bic space group Pnma with half a molecule in the asymmetric
unit. The solid-state structure is shown in Figure 1. The zirconi-
um atom is located at the symmetry centre of the molecule (a
mirror plane passes through the middle of the molecule).
Results and Discussion
As starting materials for the synthesis of zirconium-based met-
alloligands, we chose OH-functionalized triarylphosphines and
dimethyl zirconocene.[31] In previous investigations, Erker et al.
showed that phosphines linked to a ZrIV centre via an alkoxide
bridge are suitable candidates for frustrated Lewis pairs (FLPs),
which can react with nitrobenzene or activate small mole-
cules.[32] The synthesis of OH-functionalized phosphines is de-
scribed in the literature and can be easily conducted on multi-
gram scale through palladium-catalysed P–C coupling of iodo-
phenols and diphenylphosphine in dimethylacetamide
(Scheme 1).[33–35]
Figure 1. Solid-state structure of 1. Hydrogen atoms are not displayed for
clarity. Cp-atoms: C19-C24. Selected bond lengths [Š] and angles [8]: Zr1-O1
1.998(2), Zr1-O1 1.998(2), Zr1-C19 2.522(3), Zr1-C20 2.521(4), Zr1-C21
2.543(4), Zr1-C22 2.480(3), Zr1-C23 2.505(4), Zr1-C24 2.513(5); O1-Zr1-O1‘
96.71(13).
Scheme 1. Synthesis of X-(diphenylphosphino)phenols I, II and III (X=2, 3,
4).
The zirconium-oxygen bond lengths are both 1.998(2) Š, and
are similar in length to other zirconocene alkoxides.[16,36] The
O1-Zr1-O1’ bond angle (96.71(13)8) differs slightly from an
ideal tetrahedral angle, so the coordination geometry of the
zirconium centre can be best described as distorted tetrahe-
dral. The cyclopentadienyl rings coordinate to the metal in
The synthesis of the metalloligands was achieved by the
treatment of dimethyl zirconocene with [X-(diphenylphosphi-
ne)phenol] (X=2, 3, 4) I, II, and III in toluene at room tempera-
ture. The reaction of I with [Cp2ZrMe2] (Cp=h5-C5H5) yielded
the desired metalloligand [Cp2Zr(p-O-C6H4-PPh2)2] (1) within
a few minutes, as indicated by rapid gas evolution (CH4) upon
addition of the solvent (Scheme 2).
a
staggered conformation, with carbonÀzirconium bond
lengths from 2.480(3) to 2.543(4) Š. Because of the large dis-
tance between both donor sites, 1 cannot be used as a chelat-
ing ligand. However, it was used to synthesize the heterome-
tallic complex, [Cp2Zr(p-O-C6H4-PPh2-AuCl)2] (2), by a ligand ex-
change reaction with two equivalents of [AuCl(tht)] (tht=tetra-
hydrothiophene) in dichloromethane (Scheme 3).
Compound 2 can be obtained in very good yield by precipi-
tating the product with diethyl ether or by crystallization from
Scheme 2. Synthesis of the bidentate metalloligand 1.
Compound 1 can be obtained as single crystals by slow dif-
fusion of pentane into the reaction mixture. The metalloligand
was fully characterized by standard analytic and spectroscopic
1
techniques. In the H and 13C{1H} NMR spectra, a symmetric set
of resonances is observed, indicating the formation of the bi-
s(phenolate) complex. Both cyclopentadienyl units are chemi-
Scheme 3. Synthesis of the heterometallic complex 2.
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CH2Cl2/pentane. In the H NMR spectrum, the resonance corre-
are ligated in an almost linear fashion, as indicated by P-Au-Cl
bond angles of 175.92(2)8 and 179.4(2)8. Upon coordination of
the gold atoms, the O1-Zr1-O2 angle widens slightly to
98.8(4)8. Inter- or intramolecular aurophilic interactions are not
observed in the solid state.
sponding to the Cp ligands (6.38 ppm) is shifted downfield rel-
ative to that of the metalloligand 1. Upon coordination of
both AuCl units, the absolute values of the P–C coupling con-
stants in the 13C{1H} NMR spectrum are significantly increased
4
1
and range from JPC =2.3 Hz up to JPC =69.0 Hz. In the 31P{1H}
NMR spectrum, a single resonance at 31.8 ppm is observed, in-
dicating symmetric coordination of both gold atoms, and this
is shifted considerably downfield relative to that of 1 (+
38.4 ppm). The composition of the compound was confirmed
by elemental analysis and single crystal X-ray diffraction. By
slow diffusion of pentane into a saturated solution of 2 in
CH2Cl2, single crystals suitable for structural analysis were ob-
tained. The heterometallic complex crystallizes in the mono-
clinic space group P21/n with one molecule and 1.5 molecules
of CH2Cl2 in the asymmetric unit (Figure 2).
Based on these results, we felt challenged to bring both
gold atoms into closer proximity by modifying the metalloli-
gand. Hence, dimethyl zirconocene was treated with phos-
phine II to obtain the metalloligand [Cp2Zr(m-O-C6H4-PPh2)2]
(3), which is a structural isomer of 1, and features a smaller dis-
tance between both phosphine units (Scheme 4).
Complex 3 was obtained in good yield and it was fully char-
acterized by analytic and spectroscopic techniques. Resonan-
ces observed in the NMR spectra show similar shifts and cou-
pling constants to those of 1, for example, a singlet at
À5.2 ppm is observed in the 31P{1H} NMR spectrum. Subse-
quent reaction with two equivalents of [AuCl(tht)] led to the
formation of the heterometallic complex, [Cp2Zr(m-O-C6H4-
PPh2-AuCl)2] (4) (Scheme 4). During the reaction, minor decom-
position was indicated by the formation of purple gold parti-
cles. However, compound 4 can be obtained analytically pure
by crystallization from CH2Cl2/pentane. It crystallizes as small
The ZrÀO bond lengths (2.021(10) and 2.004(10) Š) are
slightly elongated compared with those of 1. For the PAuCl
units, bond lengths of 2.270(4) and 2.288(4) Š (Au-Cl), and
2.228(4) and 2.242(4) Š (PÀAu), are displayed. Both gold atoms
¯
colourless rods in the triclinic space group P1 with one mole-
cule of 4 and two molecules of CH2Cl2 in the asymmetric unit
(Figure 3).
Again, an almost linear coordination mode of both gold
atoms is observed (P1-Au1-Cl1=177.29(11)8 and P2-Au2-Cl=
171.96(11)8). The O1-Zr1-O2 bond angle (94.7(4)8) is slightly
more acute than the corresponding angles in 1 and 2. As ex-
pected, the Au-Cl bond lengths (Au1-Cl1 2.285(3) Š and Au2-
Cl2 2.292(3) Š) and the Au-P bond lengths (Au1-P1 2.231(3) Š
and Au2-P2 2.229(4) Š) do not differ significantly from those of
2. The complex was further analysed by elemental analysis and
NMR spectroscopy. A single resonance is observed at 33.1 ppm
in the 31P{1H} NMR spectrum.
Figure 2. Solid-state structure of 2. Hydrogen atoms are not displayed for
clarity. Selected bond lengths [Š] and angles [8]: Au1-Cl1 2.270(4), Au1-P1
2.228(4), Au2-Cl2 2.288(4), Au2-P2 2.242(4), Zr1-O1 2.021(10), Zr1-O2
2.004(10), P1-Au1-Cl1 179.4(2), P2-Au2-Cl2 175.92(2), O2-Zr1-O1 98.8(4).
Scheme 4. a) Synthesis of the metalloligand 3 with both phosphine groups in the meta-position and subsequent transformation to the heterometallic com-
plex 4. b) Synthesis of the metalloligand 5 with both phosphine groups in the ortho-position and subsequent transformation to the heterometallic complex
6.
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a Cl1-Au1-Au2-Cl2 torsion angle of 26.36(2)8, both PAuCl units
are nearly co-planar. The intermetallic distances are
4.4131(11) Š (Au1-Zr1) and 4.4116(12) Š (Au2-Zr1). An identical
arrangement of the heavy atoms is observed in the solid-state
structure of the pentafluorophenyl derivative 7 (Figure 5).
Hence, the assembly of these heterometallic complexes is not
significantly influenced by the nature of the anionic gold
ligand. The intermetallic distances in 7 are 4.309(2) Š (Au1-Zr1)
and 4.512(2) Š (Au2-Zr1). The angle between the heavy atoms
is 161.28(2)8, illustrating a modest deviation from linearity. This
can be explained by longer PÀAu bond lengths (2.2859(14)
and 2.2894(13) Š) than in 6. The AuÀC6F5 units are again ar-
ranged in a co-planar fashion, as indicated by the C19-Au1-
Au2-C43 torsion angle (4.48(3)8). The intermetallic distances
between gold and zirconium are longer than in systems with
attributed metallic bonding, for example, a Zr-Ru system
[Cp2Zr(CO)(m-h1(Zr),h5-C5H4)Ru(CO)2],[37] a phenomenon found
in other distal ELHB complexes as well.[1] In some cases, close
intermetallic distances in ELHB complexes can be described as
dative d10!d0 interactions. The gold–zirconium distances of
the compounds described above are in a similar range as Zr–
Ni distances, for example, in {[Cp2Zr(CH2PMe2)2]2Ni} with Zr—Ni
gaps of 4.367(1)–4.416(1) Š.[38] Although there are no signifi-
cant interactions between the gold and zirconium atoms, the
arrangement of the metal atoms might be caused by weak
electrostatic interactions between the electron-rich gold atom
and the electron-poor zirconium centre (see below for quan-
tum chemical investigations). This is supported by the fact that
the arrangement of the atoms is independent of the nature
and steric bulk of the anionic gold ligands. This is further sup-
ported by a third structure, described below, which was ob-
tained from a totally different reaction.
Figure 3. Solid-state structure of 4. Hydrogen atoms and solvent molecules
(CH2Cl2) are not displayed for clarity. Selected bond lengths [Š] and angles
[8]: Au1-Cl1 2.285(3), Au1-P1 2.231(3), Au2-Cl2 2.292(3), Au2-P2 2.229(4), Zr1-
O1 1.987(8), Zr1-O2 2.014(9), P1-Au1-Cl1 177.29(11), P2-Au2-Cl2 171.96(11),
O1-Zr1-O2 94.7(4).
In order to bring the phosphorus atoms into even closer
proximity, we synthesized the metalloligand [Cp2Zr(o-O-C6H4-
PPh2)2] (5) by the same reaction procedure described above
but this time we used phosphine III, which bears the OH
group in the ortho-position. The zirconocene complex 5 can
be obtained in good yield as colourless crystals from toluene.
In contrast to the other metalloligands, the resonance in the
31P{1H} NMR spectrum is observed at higher frequency
(À16.7 ppm), and this corresponds with the upfield resonance
of III.
Metalloligand
5
was reacted with [AuCl(tht)] and
[AuC6F5(tht)] in CH2Cl2 to obtain the heterometallic complexes,
[Cp2Zr(o-O-C6H4-PPh2-AuCl)2] (6) and [Cp2Zr(o-O-C6H4-PPh2-
AuC6F5)2] (7), respectively (Scheme 4). Both compounds were
fully characterized by analytic methods, and in both cases, the
molecular structures were determined by single crystal X-ray
diffraction. Complexes 6 and 7 crystallize in the triclinic space
¯
group P1 with one molecule of CH2Cl2 in the asymmetric unit.
Both compounds 6 and 7 were further investigated by ele-
mental analysis, IR and NMR spectroscopy. In the 31P{1H} NMR
spectra, a singlet at 23.3 ppm is observed for 6, whereas
a pseudo-quintet is seen at 34.4 ppm (with a coupling con-
stant of 8.8 Hz) for 7. The signal splitting is caused by long-
range coupling to the fluorine atoms of the C6F5 ligands, and
The solid-state structures are depicted in Figures 4 and 5.
Figure 4. Solid-state structure of 6. Hydrogen atoms and solvent molecules
(CH2Cl2) are not displayed for clarity. Selected bond lengths [Š] and angles
[8]: Au1-Cl1 2.296(2), Au1-P1 2.237(2), Au2-Cl2 2.289(2), Au2-P2 2.241(3), Zr1-
O1 2.043(6), Zr1-O2 2.034(6), O1-C1 1.322(10), O2-C19 1.340(9). P1-Au1-Cl1
175.55(10), P2-Au2-Cl2 176.00(9), O2-Zr1-O1 94.9(2).
Both compounds have similar structures, and the gold
atoms feature a linear coordination geometry in both com-
plexes. Whilst the AuÀCl, AuÀP and ZrÀO bond lengths of 6
are similar to those of its structural isomers 2 and 4, the metal
atoms are located on an almost straight line through the mole-
cule. As indicated by an Au1-Zr1-Au2 angle of 170.730(1)8, and
Figure 5. Solid-state structure of 7. Hydrogen atoms and solvent molecules
(CH2Cl2) are not displayed for clarity. Selected bond lengths [Š] and angles
[8]: Au1-P1 2.2859(14), Au1-C19 2.056(5), Au2-P2 2.2894(13), Au2-C43
2.055(4), Zr1-O1 2.042(3), Zr1-O2 2.028(3). C19-Au1-P1 173.89(15), C43-Au2-
P2 175.57(14), O2-Zr1-O1 94.38(13), C1-O1-Zr1 134.2(3), C25-O2-Zr1 135.0(3).
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this can also be observed in comparable compounds.[26,39] In
the 19F{1H} NMR spectrum, a characteristic set of signals, with
an integration ratio of 2:1:2 for the C6F5 groups, is observed at
À116.1 ppm (ortho-F), À158.8 ppm (3JFF =20.4 Hz, para-F) and
À162.3 ppm (meta-F), respectively. Upon metal coordination,
the resonances in the 31P{1H} NMR spectra are shifted signifi-
cantly downfield (+40 ppm for 6 and +51.1 ppm for 7) from
that of the free ligand 5.
Because of the close proximity of the phosphine groups in
5, and the flexibility of the ligand, we investigated whether 5
could be used as a bidentate chelating ligand. Hence, we used
[Au(tht)2][ClO4] as the gold source since both tht ligands are
easily replaced by stronger phosphine donors. The reaction be-
tween 5 and [Au(tht)2][ClO4] was conducted in CH2Cl2, and
after simple workup, the cationic heterobimetalic complex
[Cp2Zr(o-O-C6H4-PPh2)2Au][ClO4] (8) was obtained in good yield
(Scheme 5).
Figure 6. Solid-state structure of 8. Hydrogen atoms are not displayed for
clarity. Selected bond lengths [Š] and angles [8]: Au1-P1 2.2999(14), Au1-P2
2.2981(14), Zr1-O1 1.989(3), Zr1-O2 2.018(3), P2-Au1-P1 179.53(4), O1-Zr1-O2
99.32(13).
All compounds described above are based on bifunctional-
ized and coordinatively saturated zirconocene units which act
as bidentate ligands. On the other hand, a methyl zirconocene
derivative would offer the possibility of further modification of
the zirconium centre or it could be used as a precatalyst for
hydroamination or polymerization.[40,41] With this is mind, we
reacted dimethyl zirconocene with only one equivalent of III to
obtain the monofunctionalized methylzirconocene phosphine,
[Cp2ZrMe(o-O-C6H4-PPh2)] (9), as colourless single crystals from
a toluene/pentane mixture (Scheme 6).
Scheme 5. Synthesis of the ELHB complex 8.
Analysis by NMR spectroscopy revealed symmetric sets of
1
signals in both the H and 13C{1H} NMR spectra. The formation
of macrocyclic structures or polymeric chains via Au+-bridged
metalloligands 5 is not observed in solution. Instead, signal
splitting into pseudo-triplets (JPC =2.2–32.3 Hz) is observed for
the carbon atoms of the phenolate substituent. This is typically
observed for metal atoms symmetrically coordinated by two
phosphine ligands. In the 31P{1H} NMR spectrum, the chemical
shift of the phosphorus atom is 29.9 ppm (a+46.6 ppm down-
field shift relative to 5). ESI-MS experiments were conducted
and they confirm the proposed composition. The spectrum
shows a major signal at 971.11 Da, and it also displays the cor-
rect isotopic distribution. Single crystals suitable for X-ray crys-
tallography were obtained by slow diffusion of diethyl ether
into a CH2Cl2 solution of 8. The compound crystallizes in the
Scheme 6. Synthesis of the monofunctionalized zirconocene 9.
In the 1H NMR spectrum, a singlet corresponding to the
metal-bound CH3 group is observed at 0.48 ppm. The chemical
shift of the phosphorus atom is found at À16.8 ppm. Complex
9 is very sensitive to air and moisture, and decomposes with
evolution of methane within short periods of time. Single crys-
tal X-ray diffraction revealed the successful formation of the
methyl zirconocene derivative. The compound crystallizes in
¯
triclinic space group P1 with one molecule in the asymmetric
unit (Figure 6).
¯
The gold cation is coordinated in a linear fashion by both
phosphines (P1-Au1-P2=179.53(4)8), and the AuÀP bond
lengths are almost identical at 2.2999(14) Š (P1ÀAu1) and
2.2981(14) Š (P2ÀAu2), respectively. Due to the chelating metal
complexation, the O1-Zr1-O2 angle (99.32(13)8) is wider than
the corresponding angles in the other complexes, and this
demonstrates a certain flexibility of the ligand. The distance
between the gold atom and the zirconium atom is 4.094(2) Š.
Although the metalloligand 5 exhibits a certain degree of flexi-
bility, the formation of macrocyclic or oligomeric products
could not be observed.
the triclinic space group P1 with one molecule in the asym-
metric unit (Figure 7).
The Zr1ÀO1 bond length of 1.996(2) Š is significantly shorter
than the Zr1ÀC1 bond length of 2.270(3) Š. Although it is
known that zirconocene alkyl complexes can lead to the reduc-
tion of metal compounds (e.g., PbCl2),[42] we treated the mono-
dentate ligand 9 with one equivalent of [AuCl(tht)] at low tem-
perature (Scheme 7).
At À788C, no decomposition (as would be evidenced by the
reaction mixture developing a pink colour) was observed, and
after letting the reaction mixture reach room temperature,
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linear arrangement of the heavy atoms is seen (Au1-Zr1-Au2=
169.54(5)8). The intermetallic distances of Au–Zr (Au1–Zr1=
4.4105(1) Š and Au2–Zr1=4.4814(12) Š) are slightly longer
than in its structural analogues. The solid-state structure was
supported by elemental analysis and NMR spectroscopy. In the
31P{1H} NMR spectrum, a singlet is observed at 41.9 ppm, corre-
sponding to a distinctive downfield shift of +58.6 ppm relative
1
to the starting material. In the H NMR spectrum, a doublet is
Figure 7. Solid-state structure of 9. Hydrogen atoms are not displayed for
clarity. Selected bond lengths [Š] and angles [8]: Zr1-O1 1.996(2), Zr1-C1
2.270(3); O1-Zr1-C1 96.85(10).
3
seen at 0.56 ppm with a JPH coupling constant of 8.0 Hz, simi-
lar to that of [AuMe(PPh3)].[45] The presence of the AuMe
moiety is further confirmed by the 13C{1H} NMR spectrum, in
which a doublet (2JPC =98.0 Hz) is observed.
According to these results, full transmetallation and ligand
exchange took place in the reaction of a methylzirconocene
with [AuCl(tht)], and this has not been observed before. Pre-
sumably, zirconocene dichloride is formed during the reaction
and the ligand exchange reactions are in good agreement
with the HSAB principle.[46,47] It is noteworthy that since [LAu]+
species are considered isolobal with H+,[48] LAuMe complexes
can be considered isolobal with CH4.
Scheme 7. Reaction of 9 with [AuCl(tht)] yielding the heterometallic bis-
methylgold complex 10.
Quantum chemical investigation
a colourless solution was obtained. By crystallization from
CH2Cl2/pentane, colourless crystals suitable for X-ray diffraction
were obtained. Surprisingly, no heterobimetallic complex in
the form of an expected AuCl phosphine complex was ob-
tained. Instead, transmetallation and double ligand exchange
took place to give the heterometallic bis(methylgold) complex,
[Cp2Zr(o-O-C6H4-PPh2-AuCH3)2] (10). The complex crystallizes in
the monoclinic space group P21/c (Figure 8).
The nature of the Au–Zr bonding in 2, 4 and 6 was investigat-
ed by quantum chemical RI-DFT calculations (functional
BP86)[49–53] that were dispersion corrected by the D3 method of
Grimme.[54] The basis set of each atom was of def-SV(P) quali-
ty,[55,56] calculations were performed using the program system
TURBOMOLE.[57] The theoretical investigation clearly confirmed
the non-bonding situation in 2 and 4. In 6 the situation is less
obvious despite the promising concatenation of the Zr and the
two Au atoms. From an Ahlrichs–Heinzmann–Roby–Davidson
population analysis[58] the atomic charges Q were calculated to
be +1.53 (Zr) and À0.07 (Au). The shared electron number
(SEN(Au–Zr)=0.0) indicates that there is no covalent bonding
between the metal atoms. This interpretation is supported by
comparison of the Zr–Au distance (exptl 4.41 Š, calcd 4.07 Š)
with the sum of the metallic radii (about 3 Š). Presumably, the
deviation of the calculated from the experimental Au–Zr dis-
tance in 6 (4.413 Š (exptl), 4.066 Š (calcd)) results from
a metalloligand-guided crystal packing influence that exceeds
the metal–metal interaction.
Figure 8. Solid-state structure of 10. Most hydrogen atoms are not displayed
for clarity. Selected bond lengths [Š] and angles [8]: Au1-P1 2.287(3), Au1-C1
2.057(13), Au2-P2 2.302(4), Au2-C2B 2.03(4), Zr1-O1 2.040(9), Zr1-O2 2.032(9),
C1-Au1-P1 176.3(4), C2B-Au2-P2 174.0(2), O2-Zr1-O1 92.8(4).
To obtain a deeper understanding of the Zr–Au bonding we
applied the strategy which was pursued when analysing
the questionable metal–metal interaction in
Lu–Pd complex.[11] We investigated
a bimetallic
a
model compound
[Cp2ZrF2·2[P(CH3)3AuCl], in which Zr and Au are not connected
to each other through the ligand (Figure 9). The calculated Zr–
Au distances in the model and 6 (4.133 and 4.066 Š) match
each other very well. Similar results were observed for the pop-
ulation analysis (model compound: Q(Zr)= +1.59, Q(Au)=
À0.09, SEN(Zr–Au)=0.0). At large distances, the model com-
plex dissociates into the expected units composing of highly
ionic Cp2ZrF2 and two [(PMe3)AuCl] molecules (the potential
energy curve is given in Figure S1 of the Supporting Informa-
tion). Comparable to the Lu/Pd system reported before,[11] the
long-range interaction shows RÀ2 behaviour, which is typical
The solid-state structure of 10 features the same structural
arrangement observed for 6 and 7. Two phosphine-phenolate
ligands are bound to the zirconium atom. Each phosphine co-
ordinates to a AuCH3 moiety and the gold atoms are coordi-
nated in a linear fashion with bond angles of 176.3(4)8 and
174.0(2)8. As one methyl group is disordered, only the structur-
al parameters of Au1ÀC1 are discussed. The AuÀC1 distance of
2.057(13) Š (AuÀC1) is considerably shorter than the corre-
sponding bond length in [AuMe(PPh3)],[43] and more similar in
length to AuÀC bonds in Au NHC complexes.[44] Again, a near
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emitter 6 (see below). The PL maximum and efficiency appa-
rently significantly depend on the specific molecular structure.
The metalloligand 1 emits at approximately 550 nm with a PL
quantum yield of 0.24%, as determined using an integrating
sphere and excitation at 330 nm (see the Experimental Sec-
tion). The PL intensity increases by a factor of approximately
10 by decreasing the temperature to 20 K (Figure 10). The Au–
Zr compound 2 demonstrates analogous spectra and FPL =
0.68% (295 K). Despite the same composition and rather simi-
lar structure of 2 and 4 (cf. Figures 2, 3), the latter complex
shows distinct PL with bright emission at about 430 nm at
cryogenic temperatures. This shifts to about 500 nm at ambi-
ent temperature and strongly decreases in intensity. Also char-
acteristic are different PL lifetimes (extracted from biexponen-
tial fits): the emission of 1 and 2 decays at 20 K on a time scale
of tens to hundreds of ms, whereas the 430 nm band of 4
slowly decays within tens of milliseconds (contributed to com-
ponents of roughly equal amplitude with t1 =0.71 ms and t2 =
6.9 ms). At ambient temperature, both 1, 2 and 4 (the band at
500 nm) demonstrate fast PL decay within a few (sub)microsec-
onds.
Figure 9. Model system [Cp2ZrF2 2P(CH3)3AuCl] investigated to interpret
metal–metal bonding in 6.
for a charge–dipole interaction. Due to our understanding of
the Lu/Pd system, we interpret the bonding between Zr and
Au in 6 to be comparably weak.
Photophysical investigations
Figure 10 combines solid-state PL excitation (PLE) and emission
(PL) spectra of the metalloligand 1 and Au-Zr complexes 2, 4
and 6–8, measured at cryogenic (20 K) and ambient (295 K)
temperatures. The PLE spectra are rather similar, reflecting the
similar organic framework of the complexes. The onset of ab-
sorption (more steep at low temperatures) is observed at
about 350 nm for 1, 2, 4 and 8. In complexes 6 and 7 (likely
exhibiting weak Au–Zr interactions) the onset is shifted to
about 370 nm (dashed line).
The above observations likely indicate that the different
metal (Zr, Au) sites may contribute to the PL, depending on
the molecular (crystal) structure and temperature. We tenta-
tively ascribe the low-temperature band of 4 at 430 nm to
a ligand-to-metal charge-transfer (LMCT) excited state “local-
ized“ on the gold atom and phosphine ligand. On the other
hand, the emission at approximately 500–530 nm observed for
2 and 4 (at ambient temperature) may be related to the zirco-
nocene site, that is, to the emission of 1. The low-temperature
PL of bimetallic Zr–Au complex 8 at about 470 nm is particu-
larly broad and likely contributed by both metal sites (perhaps
weakly interacting due to the relatively short Zr–Au distance;
see quantum chemical investigation above). This picture seems
to be in accordance with the complex emission-wavelength-
dependent PL kinetics which were only observed for 8: the PL
at the short-wavelength edge (e.g., at 440 nm) decays within
hundreds of ms, whereas decay at longer emission wavelengths
(e.g., at 600 nm) proceeds much faster, within tens of ms.
As discussed above, trinuclear Au–Zr–Au complexes 6 and 7
exhibit a nearly identical, linear arrangement of the metal cat-
ions, which beneficially affects their photoluminescent behav-
iour, although no strong metal–metal interactions are present
in the electronic ground states based on experimental findings
and calculation (for 6). However, in our investigations the ar-
rangement of the metals presumably contributes to the partic-
ular PL properties of 6 and 7 since these complexes were
found to be the brightest emitters among the compounds
studied at cryogenic temperatures. In fact, 6 remains an effi-
cient emitter at ambient temperature, demonstrating FPL =
19% (excitation at 350 nm). The PL efficiency of 6 becomes
even larger upon cooling and approaches approximately 100%
at low temperatures (Figure 10). The PL of 6 and 7 is also dis-
tinguished by characteristic emission decay parameters: the
decay is monoexponential with t=1.05 and 0.97 ms at 20 K
and t=1.2 and 0.20 ms at ambient temperature, respectively.
Interestingly, such strongly reduced PL lifetimes at ambient
At ambient temperature, the above complexes show weak-
to-moderate phosphorescence within a spectral range of ap-
proximately 400–650 nm, with the exception of the bright
Figure 10. Photoluminescence excitation (PLE) and emission (PL) spectra of
solid complexes 1, 2, 4, 6–8 at low (20 K) and ambient temperature. PL/PLE
spectra were excited/recorded at 320 nm/emission maximum. The intensities
of the spectra are scaled for clarity.
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temperature—in relation to only moderately decreased PL in-
tensities—indicate a significant increase of the radiative decay
rate in 7 and particularly 6 by increasing the temperature.
X-ray crystallographic studies
A suitable crystal was covered in mineral oil (Aldrich) and mounted
on a glass fibre. The crystal was transferred directly to the cold
stream of a STOE IPDS 2 or a STOE StadiVari diffractometer. All
structures were solved by direct methods or by the Patterson
method (SHELXS-2013).[62] The remaining non-hydrogen atoms
were located from difference in Fourier map calculations. The re-
finements were carried out by using full-matrix least-squares tech-
niques on F, minimizing the function (F0ÀFc)2, where the weight is
Conclusions
By using OH-funtionalized triarylphosphines, dimethyl zircono-
cene was converted to three different metalloligands in which
the phosphine donor sites exhibit different spatial proximity to
each other. The metalloligands were treated with [AuCl(tht)]
and [AuC6F5(tht)] to obtain heterometallic complexes with
varying intermetallic distances. Complex 5 could also success-
fully be used as a chelating ligand to obtain the heterobimetal-
lic complex 8. By synthesizing the methylzirconocene deriva-
tive 9 and its subsequent reaction with [AuCl(tht)], full trans-
metallation as well as ligand exchange from the early to the
late transition metal was observed leading to the heterometal-
lic bis(methylgold) complex 10. The Zr-metalloligand 1, trime-
tallic and bimetallic Zr–Au complexes 2, 4, and 6–8 were inves-
tigated with respect to their photoluminescent properties. Our
results suggest that weak cooperative Zr–Au intermetallic in-
teractions, which are expected to be present in 6–8, may sig-
nificantly affect the PL properties. Quantum chemical calcula-
tions on the Au-Zr interaction were conducted and reveal
a weak interaction between the two metals. However, a de-
tailed description of those interactions and their possible ef-
fects on the excited states will require more dedicated theoret-
ical studies. An important aspect of our present work is that it
provides a structurally related set of well-characterized refer-
ence compounds for such future studies.
2
2
defined as 4F0 /2(F0 ) and F0 and Fc are the observed and calculat-
ed structure factor amplitudes using the program SHELXL-2013.[62]
Carbon-bound hydrogen atom positions were calculated. The loca-
tions of the largest peaks in the final difference Fourier map calcu-
lation as well as the magnitude of the residual electron densities in
each case were of no chemical significance. Positional parameters,
hydrogen atom parameters thermal parameters, bond lengths and
angles have been provided as Supporting Information.
Synthesis
Synthesis of [(Cp2Zr(p-OC6H4PPh2)2] (1): Dimethyl zirconocene
(200 mg, 0.79 mmol, 1.00 equiv) and 4-(hydroxyphenyl)diphenyl-
phosphine I (443 mg, 1.59 mmol, 2.00 equiv) were dissolved in tol-
uene (10 mL) and stirred at 508C for 1 h. The colourless solution
was concentrated to approximately 5 mL volume. The desired
product crystallized, overnight, by vapour diffusion of pentane into
the toluene phase. The mother liquor was decanted off and the
product was dried under vacuum. Yield: 360 mg (59%, single crys-
1
tals). H NMR (C6D6, 300 MHz): d=5.89 (s, 10H, Cp-H), 6.61–6.66 (m,
4H, CH), 7.03–7.12 (m, 12H, CH), 7.46–7.55 ppm (m, 12H, CH).
13C{1H} NMR (C6D6, 75 MHz): d=113.4 (Cp-C), 119.1 (d, 3J=8.2 Hz,
3
3
m-CPh), 126.5 (d, J=8.6 Hz, m-CPh), 128.6 (s, p-CPh), 128.8 (d, J=
6.6 Hz, o-CPh), 134.0 (d, 2J=19.2 Hz, o-CPh), 136.4 (d, 1J=21.7 Hz,
1
PC), 139.4 (d, J=12.3 Hz, PC), 166.9 ppm (s, CO). 31P{1H} NMR (C6D6,
121 MHz): d=À6.6 ppm. IR (ATR): n˜ =3113 (vw), 3050 (w), 3001
(m), 2923 (w), 1574 (m), 1541 (w), 1457 (vs.), 1431 (vs.), 1282 (vs.),
1268 (vs.), 1245 (vs.), 1180 (w), 1156 (w), 1120 (w), 1093 (w), 1067
(w), 1017 (m), 870 (s), 801 (s), 748 (vs.), 694 (s), 611 (m), 499 (m),
461 (m), 431 cmÀ1 (w). Elemental analysis calcd (%) for
[C46H38O2P2Zr] (775.98): C 71.20, H 4.94; found C 69.81, H 4.63.
Experimental Section
General procedures
All manipulations were performed under rigorous exclusion of
moisture and oxygen in flame-dried Schlenk-type glassware or in
an argon-filled MBraun glovebox. For the most part gold com-
pounds were handled with the exclusion of light by wrapping the
compound-containing flasks in aluminium foil. Prior to use, CH2Cl2
was distilled under nitrogen from CaH2. Hydrocarbon solvents (THF,
diethyl ether, n-pentane) were dried using an MBraun solvent pu-
rification system (SPS-800). Deuterated solvents were obtained
from Carl Roth GmbH (99.5 atom% D). NMR spectra were recorded
Synthesis of [(Cp2Zr(p-OC6H4PPh2)2)(AuCl)2] (2): The phosphine-
functionalized metalloligand 1 (60 mg, 0.07 mmol, 1.00 equiv) and
[AuCl(tht)] (50 mg, 0.15 mmol, 2.00 equiv) was dissolved in CH2Cl2
(5 mL) and stirred for 3 h at room temperature. The colourless solu-
tion was concentrated to 2 mL and diethyl ether (25 mL) was
added to precipitate a colourless solid. The residue was washed
with diethyl ether (2”5 mL) and dried under vacuum. Single crys-
tals suitable for X-ray analysis were obtained from slow diffusion of
1
on a Bruker Avance II 300 MHz or Avance 400 MHz. H and 13C{1H}
chemical shifts were referenced to the residual H and 13C resonan-
1
pentane into a solution of 2 in CH2Cl2. Yield: 75 mg (79%). H NMR
1
(CD2Cl2, 400 MHz): d=6.38 (s, 10H, Cp-H), 6.67–6.75 (m, 4H, CH),
7.40–7.57 ppm (m, 24H, CH). 13C{1H} NMR (CD2Cl2, 100 MHz): d=
ces of the deuterated solvents and are reported relative to tetra-
methylsilane, 31P{1H} and 19F{1H} resonances were referenced to ex-
ternal 85% phosphoric acid and CFCl3, respectively. IR spectra were
obtained on a Bruker Tensor 37. EI-mass spectra were recorded at
70 eV on a Thermo Scientific DFS. ESI mass spectra were obtained
using a FT-ICR (Fourier transform ion cyclotron resonance) IonSpec
Ultima mass spectrometer equipped with a 7 T magnet (Cryomag-
netics). FAB-Mass spectra were recorded with a Finnigan MAT90
spectrometer. Elemental analyses were carried out with an Elemen-
tar Vario EL or Micro Cube. [AuCl(tht)],[59] [Au(tht)2][ClO4],[60]
[AuC6F5(tht)][61] as well as the employed phosphines I,[34] II[35] and
III[33] were prepared according to literature procedures. Cp2ZrMe2
was purchased from Sigma–Aldrich (97%) and used as received.
1
3
114.3 (Cp-C), 117.1 (d, J=69.0 Hz, CP), 119.1 (d, J=13.4 Hz, m-CH),
129.7 (d, 3J=11.8 Hz, m-CH), 130.5 (d, 1J=62.5 Hz, PC), 132.2 (d,
2
2
4J=2.6 Hz, p-CH), 134.5 (d, J=13.6 Hz, o-CH), 136.7 (d, J=15.5 Hz,
o-CH), 169.3 ppm (d, 4J=2.3 Hz, CO). 31P{1H} NMR (CD2Cl2,
162 MHz): d=31.8 ppm. IR (ATR): n˜ =3050 (w), 1582 (vs.), 1491
(vs.), 1435 (m), 1286 (vs.), 1169 (m), 1102 (vs.), 1016 (w), 998 (w),
870 (m), 834 (m), 805 (m), 746 (m), 691 (m), 636 (vw), 617 (vw), 545
(m), 531 (w), 504 (m), 477 (w), 449 cmÀ1 (w). Elemental analysis
calcd (%) for [C46H38Au2Cl2O2P2Zr] (1240.81): C 44.53, H 3.09; found
C 44.18, H 3.16.
Synthesis of [Cp2Zr(m-OC6H4PPh2)2] (3): Dimethyl zirconocene
(182 mg, 0.72 mmol, 1.00 equiv) and 3-(hydroxyphenyl)diphenyl-
Chem. Eur. J. 2016, 22, 7115 – 7126
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phosphine II (402 mg, 1.44 mmol, 2.00 equiv) were dissolved in tol-
uene (5 mL) and stirred for 2 h at ambient temperature. By slow
diffusion of pentane into the reaction mixture, colourless crystals
were obtained. They were separated from the mother liquor by de-
cantation and dried under vacuum. Yield: 402 mg (71%, single
[AuCl(tht)] (67 mg, 0.21 mmol, 2.00 equiv) were dissolved in CH2Cl2
(5 mL) and stirred for 3 h at room temperature. The colourless solu-
tion was concentrated to 2 mL and diethyl ether (25 mL) was
added to precipitate a colourless solid. The residue was washed
with diethyl ether (2”5 mL) and dried under vacuum. Single crys-
tals suitable for X-ray analysis were obtained from slow diffusion of
pentane into a solution of 6 in CH2Cl2. Yield: 108 mg (84%).
1H NMR (CD2Cl2, 400 MHz): d=6.15 (s, 10H, Cp-H), 6.49–6.57 (m,
4H, CH), 6.79–6.87 (m, 2H, CH), 7.36–7.42 (m, 2H, CH), 7.53–
7.64 ppm (m, 20H, CH). 13C{1H} NMR (CD2Cl2, 100 MHz): d=115.2
(Cp-C), 115.9 (d, 1J=67.7 Hz, Cq), 120.2 (d, 3J=18.0 Hz, CH), 120.3
(d, J=13.1 Hz, CH), 129.5 (d, J=64.2 Hz, Cq), 129.7 (d, J=12.0 Hz,
CH), 132.5 (d, 4J=2.5 Hz, CH), 133.3 (d, 2J=6.4 Hz, CH), 134.0 (d,
4J=1.5 Hz, CH), 135.0 (d, 2J=13.9 Hz), 167.2 ppm (d, 2J=6.0 Hz,
CO). 31P{1H} NMR (CD2Cl2, 162 MHz): d=23.3 ppm. IR (ATR): n˜ =
3072 (w), 3053 (w), 1579 (m), 1480 (w), 1459 (m), 1433 (vs.), 1284
(m), 1266 (bs), 1246 (s), 1184 (w), 1154 (w), 1128 (m), 1101 (m),
1069 (w), 1023 (w), 1011 (w), 998 (w), 864 (w), 838 (w), 825 (w), 810
(s), 774 (m), 750 (s), 691 (s), 636 (vw), 598 (w), 557 (w), 528 (m), 483
(m), 445 cmÀ1 (vw). Elemental analysis calcd (%) for
[C46H38Au2Cl2O2P2Zr] (1240.81): C 44.53, H 3.09; found C 43.74, H
3.16.
1
crystals). H NMR (C6D6, 400 MHz): d=5.81 (s, 10H, Cp-H), 6.66–6.70
(m, 2H, CH), 6.80–6.85 (m, 2H, CH), 7.03–7.14 (m, 16H, CH), 7.47–
7.56 ppm (m, 8H, CH). 13C{1H} NMR (C6D6, 100 MHz): d=113.3 (Cp-
2
2
C), 119.2 (CH), 123.8 (d, J=18.1 Hz, CH), 125.3 (d, J=21.1 Hz, CH),
3
3
128.8 (s, p-CH), 128.8 (d, J=6.7 Hz, m-CH) 130.0 (d, J=8.6 Hz, CH),
2
1
1
134.3 (d, J=19.5 Hz, o-CH), 138.5 (d, J=12.6 Hz, PC), 139.0 (d, J=
12.0 Hz, PC), 166.1 ppm (d, 3J=7.9 Hz, CO). 31P{1H} NMR (C6D6,
162 MHz): d=À5.2 ppm. IR (ATR): n˜ =3049 (vw), 1572 (s), 1473 (s),
1433 (m), 1401 (s), 1271 (vs.), 1243 (s), 1156 (vw), 1090 (vw), 1068
(vw), 1015 (w), 993 (w), 915 (m), 804 (m), 784 (m), 743 (m), 693
(vs.), 620 (w), 606 (w), 539 (vw), 496 (w), 462 (vw), 417 cmÀ1 (vw).
3
1
3
Synthesis of [(Cp2Zr(m-OC6H4PPh2)2)(AuCl)2] (4): The phosphine-
functionalized metalloligand 3 (150 mg, 0.19 mmol, 1.00 equiv) and
[AuCl(tht)] (124 mg, 0.38 mmol, 2.00 equiv) were dissolved in
CH2Cl2 (5 mL) and stirred for 3 h at room temperature. After filtra-
tion, the colourless solution was concentrated to 2 mL and diethyl
ether (25 mL) is added to precipitate a colourless solid. The residue
is washed with diethyl ether (2”5 mL) and dried under vacuum.
Single crystals suitable for X-ray analysis were obtained from slow
diffusion of pentane into a solution of 2 in CH2Cl2. Yield: 212 mg
Synthesis of [(Cp2Zr(o-OC6H4PPh2)2)(AuC6F5)2] (7): The phosphine-
functionalized metalloligand 5 (75 mg, 0.09 mmol, 1.00 equiv) and
[AuC6F5(tht)] (87 mg, 0.19 mmol, 2.00 equiv) were dissolved in
CH2Cl2 (5 mL) and stirred for 3 h at room temperature. The colour-
less solution was concentrated to 2 mL and pentane (25 mL) was
added to precipitate a colourless solid. The residue was washed
with pentane (2”5 mL) and dried under vacuum. Single crystals
suitable for X-ray analysis were obtained from slow diffusion of
pentane into a solution of 7 in CH2Cl2. Yield: 130 mg (88%).
1H NMR (CD2Cl2, 400 MHz): d=5.88 (s, 10H, Cp-H), 6.50–6.54 (m,
2H, CH), 6.59 (ddd, 3J=11.7 Hz, 3J=7.7 Hz, 4J=1.6 Hz, 2H, CH),
6.80–6.90 (m, 2H, CH), 7.33–7.43 (m, 2H, CH), 7.53–7.63 (m, 12H,
CH), 7.64–7.77 ppm (m, 8H, CH). 13C{1H} NMR (CD2Cl2, 100 MHz):
1
(89%). H NMR (CD2Cl2, 400 MHz): d=6.22 (s, 10H, Cp-H), 6.65–6.72
(m, 4H, CH), 6.95 (dd, 3J=13.1 Hz, 3J=7.5 Hz, 2H, CH), 7.26–7.33
(m, 2H, CH), 7.46–7.61 ppm (m, 20H, CH). 13C{1H} NMR (CD2Cl2,
100 MHz): d=114.1 (s, Cp-C), 122.5 (d, 4J=2.2 Hz, CH), 124.1 (d,
2J=14.4 Hz, CH), 125.1 (d, 2J=12.9 Hz, CH), 129.7 (d, 3J=11.8 Hz,
1
1
CH), 129.7 (d, J=62.0 Hz, Cq), 130.0 (d, J=54.4 Hz, Cq), 131.0 (d,
3J=14.3 Hz, CH), 132.5 (d, 4J=2.5 Hz, CH), 134.7 (d, 2J=13.6 Hz,
3
CH), 166.2 ppm (d, J=15 Hz, CqO). 31P{1H} NMR (CD2Cl2, 162 MHz):
d=33.1 ppm. IR (ATR): n˜ =3050 (w), 2953 (w), 2924 (w), 1575 (S9,
1561 (s), 1543 (w), 1474 (vs.), 1461 (s), 1435 (s), 1403 (s), 1307 (s),
1275 (cs), 1250 (s), 1183 (w), 1160 (w), 1099 (s), 1014 (w), 992 (m),
924 (m), 805 (m), 785 (m), 734 (m), 710 (m), 689 (s), 618 (w), 605
(w), 588 (w), 543 (m), 504 (m), 479 (w), 432 cmÀ1 (w). Elemental
analysis calcd (%) for [C46H38Au2Cl2O2P2Zr·2CH2Cl2] (1240.81): C
40.87, H 3.00; found C 40.76, H 2.997.
1
3
d=114.8 (Cp-C), 116.9 (d, J=60.2 Hz, Cq), 120.2 (d, J=4.9 Hz, CH),
120.4 (d, J=9.3 Hz, CH), 129.8 (d, 3J=11.3 Hz, CH), 130.8 (d, J=
56.6 Hz, Cq), 132.2 (d, 4J=2.3 Hz, CH), 133.7 (d, 2J=5.5 Hz, CH),
3
1
4
2
2
134.0 (d, J=1.5 Hz, CH), 135.1 (d, J=13.8 Hz), 167.1 ppm (d, J=
6.9 Hz, CO). Carbon atoms of the C6F5 ligands cannot be observed.
31P{1H} NMR (CD2Cl2, 162 MHz): d=34.4 ppm (pseudo-quin-
tet).19F{1H} NMR (CD2Cl2, 376 MHz): d=À116.1 (m, o-F), À158.8 (t,
3J=20.4 Hz, p-F), À162.3 ppm (m, m-F). IR (ATR): n˜ =3054 (w), 1635
(vw), 1581 (w), 1561 (vw), 1501 (m), 1482 (w), 1453 (s), 1434 (vs.),
1353 (w), 1287 (m), 1267 (m), 1244 (m), 1183 (vw), 1159 (w), 1130
(w), 1100 (w), 1072 (w), 1059 (m), 1011 (w), 952 (s), 866 (m), 810 (s),
790 (w), 751 (m), 693 (s), 637 (vw), 603 (w), 555 (w), 524 (m), 483
(m), 442 cmÀ1 (vw). Elemental analysis calcd (%) for
[C58H38Au2F10O2P2Zr·CH2Cl2] (1504.03): C 44.60, H 2.54; found C
44.33, H 2.53.
Synthesis of [Cp2Zr(o-OC6H4PPh2)2] (5): Dimethyl zirconocene
(91 mg, 0.36 mmol, 1.00 equiv) and 2-(hydroxyphenyl)diphenyl-
phosphine III (200 mg, 0.72 mmol, 2.00 equiv) were dissolved in
toluene (4 mL) and stirred at 508C for 1 h. By slow diffusion of pen-
tane into the reaction mixture, colourless crystals can be obtained
which are separated from the mother liquor by decantation and
1
dried under vacuum. Yield: 194 mg (70%, single crystals). H NMR
(C6D6, 300 MHz): d=5.95 (s, 10H, Cp-H), 6.68–6.73 (m, 2H, CH), 6.94
3
3
4
(ddd, J=7.8 Hz, J=4.7 Hz, J=1.5 Hz, 2H, CH), 7.03–7.13 (m, 14H,
CH), 7.41–7.49 ppm (m, 8H, CH). 13C{1H} NMR (C6D6, 75 MHz): d=
3
114.0 (Cp-C), 119.3 (CH), 120.2 (CH), 125.3 (d, J=6.9 Hz, PCq), 128.8
Synthesis of [(Cp2Zr(o-OC6H4PPh2)2)Au][ClO4] (8): The phosphine-
functionalized metalloligand 5 (50 mg, 0.06 mmol, 1.00 equiv) and
[Au(tht)2][ClO4] (30 mg, 0.06 mmol, 1.00 equiv) were dissolved in
CH2Cl2 (5 mL) and stirred for 3 h at room temperature under exclu-
sion of light. The colourless solution was dried under vacuum and
the residue was washed with diethyl ether. The product was ob-
tained as a colourless powder after drying again under high
vacuum. Single crystals suitable for X-ray analysis were obtained
from slow diffusion of diethyl ether into a solution of 7 in CH2Cl2/
3
(d, J=6.8 Hz, m-CPh), 128.8 (s, p-CPh), 131.0 (s, CH), 133.6 (s, CH),
2
1
134.5 (d, J=19.8 Hz, o-CPh), 138.2 (d, J=11.7 Hz, PCq), 168.5 ppm
(d, 2J=18.2 Hz, CO). 31P{1H} NMR (C6D6, 121 MHz): d=À16.7 ppm.
IR (ATR): n˜ =3049 (vw), 2999 (m), 1574 (m), 1560 (m), 1476 (w),
1458 (vs.), 1431 (vs.), 1285 (vs.), 1277 (vs.), 1266 (vs.), 1245 (vs.),
1180 (w), 1156 (w), 1120 (w), 1089 (w), 1067 (w), 1022 (w), 1013 (w),
875 (m), 866 (m), 829 (vw), 811 (s), 799 (vs.), 745 (vs.), 729 (w), 694
(s), 677 (w), 612 (m), 500 (m), 461 (m), 431 cmÀ1 (w). FAB-MS: m/z
[MÀC6H4PPh2]+: 513.1, 514.1, 515.1. Elemental analysis calcd (%) for
[C46H38O2P2Zr] (775.98): C 71.20, H 4.94; found C 70.71, H 4.91.
1
acetonitrile. Yield: 62 mg (90%). H NMR (CD2Cl2, 400 MHz): d=5.98
(s, 10H, Cp-H), 6.58–6.66 (m, 2H, CH), 6.79–6.84 (m, 2H, CH), 6.92–
6.97 (m, 2H, CH), 7.52–7.64 ppm (m, 22H, CH). 13C{1H} NMR (CD2Cl2,
100 MHz): d=114.5 (s, Cp), 115.0 (t, J=32.3 Hz, Cq), 120.3 (t, J=
Synthesis of [(Cp2Zr(o-OC6H4PPh2)2)(AuCl)2] (6): The phosphine-
functionalized metalloligand 5 (81 mg, 0.10 mmol, 1.00 equiv) and
Chem. Eur. J. 2016, 22, 7115 – 7126
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2.2 Hz, CH), 120.7 (t, J=4.6 Hz, CH), 129.3 (t, J=30.0 Hz, Cq), 130.4
(t, J=5.8 Hz, CH), 133.0 (s, 2xCH, overlapping), 134.8 (d, J=7.6 Hz,
CH), 135.4 (s, CH), 167.3 ppm (t, J=4.3 Hz, CqO). 31P{1H} NMR
(CD2Cl2, 162 MHz): d=29.9 ppm. IR (ATR): n˜ =3013 (vw), 2966 (w),
2873 (w), 1508 (w), 1457 (s), 1435 (s), 1396 (vs.), 1295 (m), 1264 (w),
1092 (vs.), 873 (w), 809 (w), 748 (w), 691 (w), 619 (w), 519 (w), 486
(w), 458 (vw), 415 cmÀ1 (vw). ESI-MS: m/z [M]+: calcd 971.1060;
found 971.11, 972.11, 973.11, 974.11, 975.11, 976.11, 977.11, 978.11,
979.11 (isotopic pattern). Elemental analysis calcd (%) for
[C46H38AuClO6P2Zr] (1072.39): C 51.52, H 3.57; found C 50.96, H
3.70.
Crystal data
Crystal data for C46H38O2P2Zr (1) (M=775.92 gmolÀ1): orthorhom-
bic, space group Pnma (no. 62), a=12.490(3) Š, b=39.145(8) Š, c=
7.8589(16) Š, V=3842.3(13) Š3, Z=4, T=120.15 K, m(MoKa)=
, D , 10324 reflections measured
0.407 mmÀ1 calcd =1.341 gcmÀ3
(4.1628ꢀ2Vꢀ50.7648), 3568 unique (Rint =0.0658, Rsigma =0.1052)
which were used in all calculations. The final R1 was 0.0358 (I>
2s(I)) and wR2 was 0.0645 (all data).
Crystal data for C47.5H41Au2Cl5O2P2Zr (2) (M=1368.14 gmolÀ1): mon-
oclinic, space group P21/n (no. 14), a=12.307(3) Š, b=21.800(4) Š,
c=21.063(4) Š, b=105.07(3)8, V=5457(2) Š3, Z=4, T=200.15 K,
m(MoKa)=5.888 mmÀ1, Dcalcd =1.665 gcmÀ3, 24274 reflections mea-
Synthesis of [Cp2Zr(Me)(o-OC6H4PPh2)] (9): Dimethyl zirconocene
(200 mg, 0.79 mmol, 1.00 equiv) and 2-(hydroxyphenyl)diphenyl-
phosphine (221 mg, 0.79 mmol, 1.00 equiv) were suspended in tol-
uene (3 mL). The suspension was warmed until a clear solution
was obtained. By slow diffusion of pentane into the reaction mix-
ture, colourless crystals were obtained. They were separated from
the mother liquor by decantation and dried under vacuum. Yield:
sured (3.7368ꢀ2Vꢀ52.038), 10644 unique (Rint =0.1204, Rsigma
=
0.1255) which were used in all calculations. The final R1 was 0.0739
(I>2s(I)) and wR2 was 0.2033 (all data).
Crystal data for C48H42Au2Cl6O2P2Zr (4) (M=1410.61 gmolÀ1): triclin-
ic, space group P1 (no. 2), a=8.5826(17) Š, b=14.031(3) Š, c=
¯
21.075(4) Š, a=98.45(3)8, b=96.69(3)8, g=107.05(3)8, V=
1
286 mg (70%, single crystals). H NMR (C6D6, 300 MHz): d=0.48 (s,
2365.8(9) Š3, Z=2, T=103.15 K, m(MoKa)=6.848 mmÀ1
, Dcalcd =
3
3
4
3H, CH3), 5.75 (s, 10H, Cp-H), 6.59 (ddd, J=8.0 Hz, J=5.0 Hz, J=
1.980 gcmÀ3
,
21779 reflections measured (3.348ꢀ2Vꢀ52.238),
3
3
0.9 Hz, 1H, CH), 6.67–6.72 (m, 1H, CH), 6.88 (ddd, J=7.6 Hz, J=
4.3 Hz, 4J=1.6 Hz, 1H, CH), 7.04–7.14 (m, 7H, CH), 7.38–7.45 ppm
(m, 4H, CH). 13C{1H} NMR (C6D6, 75 MHz): d=24.3 (CH3), 111.6 (Cp-
C), 118.4 (d, J=1.7 Hz), 120.1 (CH), 125.1 (d, J=7.6 Hz, PCq), 128.7
(d, J=4.7 Hz, m-CPh), 128.8 (s, p-CPh), 130.7 (s, CH), 133.7 (s, CH),
9210 unique (Rint =0.1180, Rsigma =0.1700) which were used in all
calculations. The final R1 was 0.0541 (I>2s(I)) and wR2 was 0.1118
(all data).
Crystal data for C47H40Au2Cl4O2P2Zr (6) (M=1325.68 gmolÀ1): triclin-
3
3
3
¯
2
1
ic, space group P1 (no. 2), a=10.729(2) Š, b=15.006(3) Š, c=
134.5 (d, J=19.9 Hz, o-CPh), 138.1 (d, J=11.9 Hz, PCq), 167.9 ppm
(d, 2J=18.3 Hz, CO). 31P{1H} NMR (C6D6, 121 MHz): d=À16.8 ppm.
IR (ATR): n˜ =3066 (w), 3052 (w), 2999 (w), 2922 (w), 2868 (w), 1576
(m), 1475 (w), 1458 (vs.), 1431 (vs.), 1408 (w), 1306 (w), 1289 (vs.),
1272 (m), 1252 (m), 1180 (w), 1159 8w), 1139 (w), 1121 (w), 1097
(w), 1067 (w), 1035 (w), 1014 (m), 881 (m), 803 (s), 758 (s), 748 (s),
730 (s), 696 (s), 622 (w), 503 (w), 493 (w), 473 (w), 458 (w),
429 cmÀ1 (w). FAB-MS: m/z [MÀCH3]+: 497.0, 498.1, 499.0, 500.0,
501.0 (isotopic pattern). EI-MS: m/z [MÀCH3]+: 497.192, 498.194,
499.193, 500.193. Elemental analysis calcd (%) for [C29H27OPZr]
(513.73): C 67.80, H 5.30; found C 65.41, H 4.88. The compound
was found to be repeatedly low in carbon in the microanalysis.
15.187(3) Š, a=70.21(3)8, b=75.39(3)8, g=82.24(3)8, V=
2222.9(9) Š3, Z=2, T=100.15 K, m(MoKa)=7.165 mmÀ1
, Dcalcd =
1.981 gcmÀ3, 20445 reflections measured (2.8888ꢀ2Vꢀ52.0848),
8690 unique (Rint =0.0690, Rsigma =0.1126) which were used in all
calculations. The final R1 was 0.0416 (I>2s(I)) and wR2 was 0.0913
(all data).
Crystal data for C59H40Au2Cl2F10O2P2Zr (7) (M=1588.90 gmolÀ1): tri-
¯
clinic, space group P1 (no. 2), a=13.880(3) Š, b=13.924(3) Š, c=
17.149(3) Š, a=104.51(3)8, b=93.44(3)8, g=119.42(3)8, V=
2728.2(12) Š3, Z=2, T=100.15 K, m(MoKa)=5.786 mmÀ1
, Dcalcd =
1.934 gcmÀ3, 23885 reflections measured (3.4168ꢀ2Vꢀ52.1088),
10644 unique (Rint =0.0511, Rsigma =0.0611) which were used in all
calculations. The final R1 was 0.0291 (I>2s(I)) and wR2 was 0.0612
(all data).
Synthesis of [(Cp2Zr(o-OC6H4PPh2)2)(AuCH3)2] (10): The monofunc-
tionalized metalloligand 9 (50 mg, 0.10 mmol, 1.00 equiv) and
[AuCl(tht)] (33 mg, 0.10 mmol, 1.00 equiv) were cooled to À788C in
a Schlenk tube. CH2Cl2 (3 mL) was slowly added and the colourless
solution was stirred at low temperature for one hour. After warm-
ing to room temperature, the clear solution was carefully layered
with diethyl ether. After a few days, colourless crystals were ob-
served on the glass wall. They were separated from the mother
liquor by decantation and finally dried under high vacuum. Yield:
Crystal data for C46H38AuClO6P2Zr (8) (M=1072.34 gmolÀ1): triclinic,
¯
space group P1 (no. 2), a=11.839(2) Š, b=12.774(3) Š, c=
15.225(3) Š, a=75.87(3)8, b=79.14(3)8, g=69.33(3)8, V=
2075.9(9) Š3, Z=2, T=100.15 K, m(MoKa)=3.971 mmÀ1
, Dcalcd =
1.716 gcmÀ3, 27424 reflections measured (3.4748ꢀ2Vꢀ528), 8155
unique (Rint =0.0772, Rsigma =0.0682) which were used in all calcula-
tions. The final R1 was 0.0336 (I>2s(I)) and wR2 was 0.0750 (all
data).
1
28 mg (50%, single crystals). H NMR (CD2Cl2, 400 MHz): d=0.56 (d,
3J=8.0 Hz, 6H, AuCH3), 6.06 (s, 10H, Cp-H), 6.47–6.55 (m, 4H, CH),
6.75–6.82 (m, 2H, CH), 7.32 (dt, 3J=7.9 Hz, 4J=1.1 Hz, 2H, CH),
7.43–7.70 ppm (m, 20H, CH). 13C{1H} NMR (CD2Cl2, 100 MHz): d=7.1
Crystal data for C29H27OPZr (9) (M=513.69 gmolÀ1): triclinic, space
¯
group P1 (no. 2), a=10.363(2) Š, b=10.797(2) Š, c=12.432(3) Š,
2
3
a=85.34(3)8, b=74.50(3)8, g=61.54(3)8, V=1176.6(5) Š3, Z=2, T=
110.15 K, m(MoKa)=0.552 mmÀ1, Dcalcd =1.450 gcmÀ3, 10368 reflec-
tions measured (4.598ꢀ2Vꢀ52.8188), 4592 unique (Rint =0.0462,
(d, J=98 Hz, CH3), 114.8 (Cp-C), 120.0 (d, J=7.3 Hz, CH), 120.1 (d,
3J=4.4 Hz, CH), 129.4 (d, J=10.6 Hz, m-CH), 131.4 (d, J=2.0 Hz, p-
3
4
1
3
3
CH), 132.6 (d, J=43.0 Hz, PCq), 132.9 (d, J=4.2 Hz), 133.5 (d, J=
5.0 Hz), 135.2 ppm (d, 2J=13.9 Hz, o-CH). Due to poor solubility,
two quaternary carbon atoms could not be detected. 31P{1H} NMR
(CD2Cl2, 162 MHz): d=41.9 ppm. IR (ATR): n˜ =3049 (w), 3007 (w),
2964 (w), 2907 (vw), 1494 (w), 1476 (w), 1459 (s), 1434 (vs.), 1396
(m), 1363 (w), 1301 (m), 1284 (m), 1268 (m), 1248 (s), 1182 (vw),
1156 (w), 1126 (w), 1100 (m), 1068 (m), 1015 (m), 866 (m), 812 (s),
752 (m), 695 (m), 636 (vw), 600 (w), 555 (w), 521 (m), 484 (m),
446 cmÀ1 (vw). Elemental analysis calcd (%) for [C48H44Au2O2P2Zr]
(1199.98): C 48.04, H 3.70; found C 47.41, H 3.60.
Rsigma =0.0712) which were used in all calculations. The final R1 was
0.0332 (I>2s(I)) and wR2 was 0.0693 (all data).
Crystal data for C48H44Au2O2P2Zr (10) (M=1199.92 gmolÀ1): mono-
clinic, space group P21/c (no. 14), a=16.916(3) Š, b=14.338(3) Š,
c=17.689(4) Š, b=101.84(3)8, V=4199.0(15) Š3, Z=4, T=100.15 K,
m(MoKa)=7.329 mmÀ1, Dcalcd =1.898 gcmÀ3, 20285 reflections mea-
sured (3.6888ꢀ2Vꢀ52.2148), 8208 unique (Rint =0.0819, Rsigma
=
0.0891) which were used in all calculations. The final R1 was 0.0736
(I>2s(I)) and wR2 was 0.2115 (all data).
Chem. Eur. J. 2016, 22, 7115 – 7126
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