Synthesis, structure and transmetalation activity of various C,Y-chelated organogold(I) compounds

Article abstract of DOI:10.1002/ejic.201200152

A set of organogold(I) compounds L^1-4Au(PPh₃), where L¹ = [o-C₆H₄(CH=NC₆H ₃iPr₂-2,6)]^- (1), L² = {o,o-C ₆H₃[C(Me)=NC₆H₃Me ₂-2,6]₂}^- (2), L³ = [o,o'-C ₆H₃(CH₂OMe)(CH₂NMe ₂)]^- (3), L⁴ = [o,o-C₆H ₃(CH₂OMe)₂]^- (4), were synthesized by the reaction of parent organolithium derivatives L^1-4Li with [AuCl(PPh₃)] in good yields. The molecular structures of 1-4 were characterized by ESI mass spectrometry and ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy, and their structures in the solid state were determined using single-crystal X-ray diffraction analyses. The transmetalation potential of 1-4 was tested by the reaction with either [PdCl₂(CH₃CN)₂] or [PtCl₂(Et ₂S)₂] complexes. While the reaction of compounds 1 and 2 proceeded smoothly with the formation of the desired transition-metal complexes, i.e. (L¹PdCl)₂ (5), L¹PtCl(Et₂S) (6) and L²MCl [M = Pd (7) or Pt (8). In the case of the O,C,N- and O,C,O-chelated derivatives 3 and 4 only the platinum(II) compounds L ³PtCl(PPh₃) (9) and L⁴PtCl(Et ₂S)₂ (10) could be isolated after the reaction, as a result of the labile behaviour of the corresponding palladium compounds. All derivatives 5-10 were characterized by the help of ESI mass spectrometry and ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy, and in the case of compounds 5-7 and 9 using single-crystal X-ray diffraction analyses. Copyright

Full text of DOI:10.1002/ejic.201200152

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FULL PAPER
DOI: 10.1002/ejic.201200152
Synthesis, Structure and Transmetalation Activity of Various C,Y-Chelated
Organogold(I) Compounds
[a]
[a]
[a]
[a]
[b]
ˇ
˚ˇ ˇ
Martin Hejda, Libor Dostál,* Roman Jambor, Ales Ruzicka, Robert Jirásko, and
[a]
ˇ
Jaroslav Holecek
Keywords: Gold / Palladium / Platinum / Metalation / Chelates
A set of organogold(I) compounds L1–4Au(PPh3), where L1
[o-C6H4(CH=NC6H3iPr2-2,6)]– (1), L2 = {o,o-C6H3[C(Me)=
NC6H3Me2-2,6]2}– (2), L3
[o,oЈ-C6H3(CH2OMe)(CH2N-
=
1 and 2 proceeded smoothly with the formation of the desired
transition-metal complexes, i.e. (L1PdCl)2 (5), L1PtCl(Et2S) (6)
and L2MCl [M = Pd (7) or Pt (8). In the case of the O,C,N-
and O,C,O-chelated derivatives 3 and 4 only the platinum(II)
compounds L3PtCl(PPh3) (9) and L4PtCl(Et2S)2 (10) could be
isolated after the reaction, as a result of the labile behaviour
of the corresponding palladium compounds. All derivatives
5–10 were characterized by the help of ESI mass spectrome-
try and 1H NMR, 13C NMR and 31P NMR spectroscopy, and
in the case of compounds 5–7 and 9 using single-crystal X-
ray diffraction analyses.
=
Me2)]– (3), L4 = [o,o-C6H3(CH2OMe)2]– (4), were synthesized
by the reaction of parent organolithium derivatives L1–4Li
with [AuCl(PPh3)] in good yields. The molecular structures
of 1–4 were characterized by ESI mass spectrometry and 1H
NMR, 13C NMR and 31P NMR spectroscopy, and their struc-
tures in the solid state were determined using single-crystal
X-ray diffraction analyses. The transmetalation potential of
1–4 was tested by the reaction with either [PdCl2(CH3CN)2]
or [PtCl2(Et2S)2] complexes. While the reaction of compounds
Introduction
The chemistry of the so called Y,C,Y (Y,Y,Y) pincer-type
coordinating ligands (Y = donor atom such as N, P, O etc.)
represents a rapidly developing area of chemical research in
the field of organometallic chemistry and catalysis.[1] Al-
though the chemistry of transition metals was preferred at
the beginning of the research in this field,[2] later the investi-
gation of main-group metal compounds became important
and interesting findings were reported.[3] The key influence
of the pincer ligand is stabilization of the central metal by
two dative connections YǞM between the metal and donor
atoms Y. Thus, it is necessary to metalate the pincer ligand
backbone to the ortho-ortho position to profit from these
intramolecular interactions (Figure 1, L2–4). Several reac-
tion pathways were developed for successful metalation of
the pincer ligand (Scheme 1), these comprise of (i) direct
cyclometalation,[4] which include C–H bond activation and
no prefunctionalization of the ligand is necessary. (ii) Oxi-
dative addition[5] of low valent metal precursors into a C–X
bond (X = Br, I). (iii) Transcyclometalation,[6] which is the
Figure 1. Ligands used in this study.
substitution of one pincer-type ligand for another. (iv)
Transmetalation, this method requires preparation of well-
defined main-group metal precursors,[7] which further react
with metal halides with elimination of main-group metal
halides. The transmetalation procedure is the best choice,
especially for main-group metal compounds and for transi-
tion-metal complexes of N,C,N pincer-type ligands that do
not undergo easy cyclometalation as do their P,C,P or S,C,S
counterparts.[8] Van Koten et al. have reported on a new
synthetic strategy leading to organometallic N,C,N pincer
[a] Department of General and Inorganic Chemistry,
Faculty of Chemical Technology, University of Pardubice,
Studentská 573, 53210 Pardubice, Czech Republic
Fax: +420-466037068
E-mail: libor.dostal@upce.cz
[b] Department of Analytical Chemistry,
Faculty of Chemical Technology, University of Pardubice,
Studentská 573, 53210 Pardubice, Czech Republic
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200152.
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L. Dostál et al.
FULL PAPER
compounds using organogold(I) precursors[9] as the trans- we report here on the preparation of four organogold(I)
metalating reagents. The gold fragment AuL+ has an isolo- compounds L1–4Au(PPh3), where L1
[o-C6H4-
bal relationship to Li+, which indicates that the [RAuL] (CH=NC6H3iPr2-2,6)]– (1), L2
{o,o-C6H3[C(Me)=
compounds could have similar transmetalating properties NC6H3Me2-2,6]2}– (2), L3
[o,oЈ-C6H3(CH2OMe)-
=
=
=
as the corresponding organolithium RLi reagents. These (CH2NMe2)]– (3) and L4 = [o,o-C6H3(CH2OMe)2]– (4) (Fig-
gold synthons also have several advantages in comparison ure 1, Scheme 2). This set of gold(I) synthons enables us
with commonly used N,C,N-chelated organolithium com- to question two basic problems, (i) is the transmetalation
pounds such as stability towards air and moisture, nontox- possible using only a bidentate ligand such as L1, (ii) is it
icity, redox stability, high yield transmetalation procedures possible to use this synthetic protocol for ligands substi-
and recycling of gold reagents. Since the first report on the tuted by oxygen donor atoms (L3,4), which are in general
transmetalation properties of organogold(I) derivatives of not well suited for coordination of late transition metals?
the classical N,C,N pincer-type ligand {[o,o-C6H4- Thus, the first attempts to use 1–4 as transmetaling agents
(CH2NMe2)2]–},[10] the same working team has enriched using [PdCl2(CH3CN)2] and [PtCl2(Et2S)2] complexes as the
this family of gold reagents to those derived from Phebox substrates are described. Reported compounds were charac-
ligands. A variety of transition-metal halides (both early terized by elemental analysis, electrospray mass spectrome-
and late) were used as substrates for transmetalation stud- try (ESI), multinuclear NMR spectroscopy and single-crys-
ies.[11] It is worth noting that some silver(I) pincer com- tal X-ray diffraction analyses.
pounds were used by van der Vlugt et al. for the prepara-
tion of palladium(II) complexes.[12]
Scheme 2. Preparation of organogold(I) precursors 1–4.
Results and Discussion
Organogold(I) Precursors: Syntheses, Characterization and
Structure
Organogold(I) precursors 1–4 were prepared by standard
procedures; treating the starting organolithium precursors
L1–4Li with one molar equiv. of commercially available
[AuCl(PPh3)] according to Scheme 2. All compounds were
obtained in good yields as white or yellowish (2) crystalline
solids, which are very soluble in both aromatic and chlori-
nated solvents. The identity of 1–4 was established by satis-
factory elemental analysis and ESI mass spectrometry,
where the presence of protonated molecules [M + H]+ and/
(or) sodium (potassium) adducts [M + Na]+ or [M + K]+
1
were detected. The H NMR and 13C NMR spectra of 1–4
revealed the expected set of signals from the ligands L1–4
and PPh3 (see Exp. Section). The 31P NMR spectra con-
tained one signal for each compound (δ = 44.1 for 1, 41.9
for 2, 44.9 for 3 and 44.4 ppm for 4), which are slightly
shifted to lower field in comparison with the starting
chlorido complex [AuCl(PPh3)] (δ = 32.7 ppm).
The molecular structures of 1–4 were unambiguously de-
termined by the help of single-crystal X-ray diffraction
Scheme 1. Synthetic strategies for metalation of the pincer ligand
backbone.
We are interested in the pincer chemistry of main-group analyses. The crystallographic data are given in the Exp.
metals and during these investigations new types of Section and the molecular structures of 1–4 are illustrated
O,C,O,[13] N,C,O[14] and N,C,N[15] and potentially bidentate in Figures 2 and 3, together with the relevant structural pa-
N,C[16] ligands were introduced. Organometallic derivatives rameters given in the figure captions. All of the molecular
of these ligands were exclusively prepared starting from the structures are closely related. The central gold atom is η1-
organolithium precursors using a standard transmetalation C-bonded to the C-ipso atom of the corresponding ligand
synthetic protocol. We are interested in whether it is feasible (L1–4) and the triphenylphosphane molecule is coordinated
to prepare organogold(I) derivatives of our ligands and to in the trans position [the range of the P–Au bond lengths is
use them as transmetalating agents in the reactions with 2.2742(9)–2.2851(15) Å] with the bond angles P–Au–C in
transition-metal halides. As the first part of these studies, the range of 174.2(4)–179.21(12)° in 1–4. The arms of the
2
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Various Chelated Organogold(I) Compounds
donor ligands remain noncoordinated to the gold atom in
all cases. The molecular structures of compounds 1–4 are
analogous to the other organogold(I) compounds contain-
ing a Y,C,Y-chelating ligand reported earlier.[10,11]
Figure 3. ORTEP diagram of compounds 3 (top) and 4 (bottom)
with thermal displacement parameters at 30% probability. Selected
distances [Å] and angles [°] for 3: Au1–C1 2.042(5), Au1–
P1 2.2786(14), C1–Au1–P1 179.21(12). For 4: Au1–C1 2.053(6),
Au1–P1 2.2851(15), C1–Au1–P1 175.76(16).
Figure 2. ORTEP diagram of compounds 1 (top) and 2 (bottom)
with thermal displacement parameters at 30% probability, hydro-
gen atoms and the toluene molecule in the case of 2 were omitted
for clarity. Selected distances [Å] and angles [°] for 1: Au1–
C1 2.019(13), Au1–P1 2.275(3), C1–Au1–P1 174.2(4). For 2: Au1–
C1 2.067(4), Au1–P2 2.2742(9), C1–Au1–P2 176.54(9).
Transmetalation Using Organogold(I) Compounds 1–4
Scheme 3. Preparation of 5 and 6.
The transmetalation attempts are described consecutively
according to the ligand used (L1–4), because the results dif-
fer substantially in most cases.
only one signal at δ = 32.7 ppm for [AuCl(PPh3)] proving
The reaction of compound
1 with both [PdCl2- that all starting material was consumed. After workup,
(CH3CN)2] and [PtCl2(Et2S)2] proceeded smoothly giving compounds 5 and 6 were isolated in 30% and 78% yield,
compounds (L1PdCl)2 (5) and L1PtCl(Et2S) (6), respectively respectively. The lower isolated yield in the case of 5 was
(Scheme 3). The reaction was monitored by 31P NMR as caused mainly by a rather similar solubility of 5 and incipi-
1
well as H NMR spectroscopy, which indicated essentially ent [AuCl(PPh3)]. Both compounds were characterized by
quantitative conversion. The 31P NMR spectrum revealed elemental analysis and ESI mass spectrometry, where ions
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[M – Cl]+ or their water adducts [M – Cl + H2O]+ were
1
detected. The H NMR and 13C NMR spectrum of 5 con-
tained one set of expected signals corresponding to the li-
gand L1. On the contrary, the 1H NMR and 13C NMR
spectra of 6 contained, besides the signals of the ligand L1,
signals from the coordinated diethylsulfide molecule.
The presence of an intramolecular NǞM interaction was
reflected by the observation of two signals for the magneti-
cally nonequivalent methyl groups of the iPr moieties in the
1H NMR and 13C NMR spectra of 5 and 6, which is consis-
tent with the hindered rotation around the aryl–N bond.
These findings indicate that the acetonitrile molecules are
lost during the reaction of 1 with [PdCl2(CH3CN)2], on the
contrary one of the diethyl sulfide molecules remains intact
at the platinum centre in the case of the formation of 6 from
1 and [PtCl2(Et2S)2]. It is also worth noting that compound
5 has recently been prepared by Chang et al. using standard
cyclometalation procedures starting from L1H, Na2[PdCl4]
and sodium acetate as the base.[17] Nevertheless, the molec-
ular structure of 5 has not been reported.
Figure 4. ORTEP diagram of compound 5 with thermal displace-
ment parameters at 30% probability, hydrogen atoms were omitted
for clarity. Symmetry operator: a = –x, 1 – y, –z. Selected distances
[Å] and angles [°]: Pd1–C1 1.963(12), Pd1–N1 2.0187(18), Pd1–
Cl1 2.3264(6), Pd1–Cl1a 2.4493(6), C1–Pd1–Cl1a 173.07(7), N1–
Pd1–Cl1 176.19(5).
The molecular structures of 5 and 6 were established by
single-crystal X-ray diffraction analyses, the crystallo-
graphic data are given in the Exp. Section and the molecu-
lar structures are depicted in Figures 4 and 5 together with
relevant structural parameters summarized in the figure
captions. Compound 5 is built up as a centrosymmetric di-
meric molecule with the chlorine atoms Cl1 and Cl1a lo-
cated in the bridging positions. These bridges are slightly
nonsymmetric as documented by the bond lengths Pd1–Cl1
2.3264(6) and Pd1–Cl1a 2.4493(6) Å. Similar dimeric units
are usually formed in analogous N,C-chelated palladium(II)
compounds.[17] The pendant arm of the ligand is coordi-
nated to the palladium atom [the bond length Pd1–N1 is
2.0187(18) Å]. The central palladium atom is situated in a
square-planar environment with the N1, Cl1 and C1, Cl1a
atoms placed mutually in trans positions [the bond angles
are C1–Pd1–Cl1a 173.07(7) and N1–Pd1–Cl1 176.19(5)°].
In contrast to 5, compound 6 retains a monomeric struc-
ture in the solid state (Figure 5), because the fourth coordi-
nation place in the square-planar environment of the cen-
tral platinum atom is occupied by a diethyl sulfide donor
molecule [the bond length Pt1–S1 is 2.2643(13) Å]. This an-
cillary ligand is coordinated in the trans position to the ni-
trogen atom N1 [bond length Pt1–N1 is 2.031(4) Å and
bond angle S1–Pt1–N1 is 173.66(13)°].
Figure 5. ORTEP diagram of compound 6 with thermal displace-
ment parameters at 30% probability, hydrogen atoms were omitted
for clarity. Selected distances [Å] and angles [°]: Pt1–C1 1.981(5),
Pt1–N1 2.031(4), Pt1–Cl1 2.3849(13), Pt1–S1 2.2643(13), C1–Pt1–
Cl1 173.12(16), N1–Pt1–S1 173.66(13).
Analogous to 1, transmetalation using compound 2 sub-
stituted by the pincer-type ligand L2 resulted in the prepa-
ration of L2MCl [M = Pd (7) or Pt (8)], this was followed
by 31P NMR and 1H NMR spectroscopy (Scheme 4). How-
ever, the isolated yields of 7 (56%) and 8 (61%) are not
quantitative mainly because of the rather similar solubility
with the byproduct [AuCl(PPh3)], which complicated
crystallization of the products from the reaction mixtures.
Scheme 4. Preparation of 7 and 8.
Both compounds displayed satisfactory elemental analysis which is consistent with a rigid tridentate NCN coordina-
and corresponding positive-ion full-scan ESI mass spectra tion of the ligand L2 and square-planar environment
showed ions [M – Cl]+ or their water adducts [M – Cl + around the central palladium or platinum atoms, which is
1
H2O]+. The H NMR and 13C NMR spectra of 7 and 8 usual in this class of compounds containing related bis-
contained one set of signals corresponding to the ligand L2, (aldimine) N,C,N pincer-type ligands.[18]
4
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Various Chelated Organogold(I) Compounds
The molecular structure of 7 was established by the help sumption was verified, because addition of one molar equiv.
of single-crystal X-ray diffraction analysis; the crystallo- of PPh3 into the reaction mixture significantly improved the
graphic data are given in the Exp. Section and the molecu- yield of 9 (isolated yield 69%, Scheme 5). Compound 9 dis-
lar structure is shown in Figure 6 together with relevant played satisfactory elemental analysis and its positive-ion
structural parameters summarized in the figure caption. full-scan ESI mass spectrum revealed the ion [M – Cl]+ at
1
The molecular structure of compound 7 is closely related m/z = 635. The H NMR and 13C NMR spectra of 9 con-
to other palladium(II) pincer-type complexes.[18] The pincer tained one set of signals, which is consistent with the pro-
ligand is coordinated to the central atom in a meridional posed structure and proved the presence of coordinated
fashion through a NCN donor set with two strong NǞPd PPh3 (see Exp. Section.)
intramolecular interactions [the bond lengths are Pd1–N1
2.075(4), Pd1–N2 2.068(3) Å]. The remaining coordination
position in the square-planar geometry around the central
palladium atom is filled by the chlorine atom Cl1, which is
situated in the trans position to the C-ipso atom of the li-
gand [the bond angle is 177.89(13)°].
Scheme 5. Preparation of 9.
The molecular structure of 9 was established by a single-
crystal X-ray diffraction analysis, the crystallographic data
are given in the Exp. Section and the molecular structure is
shown in Figure 7 together with relevant structural param-
eters summarized in the figure caption.
Figure 6. ORTEP diagram of compound 7 with thermal displace-
ment parameters at 30% probability, hydrogen atoms were omitted
for clarity. Selected distances [Å] and angles [°]: Pd1–C1 1.898(4),
Pd1–N1 2.075(4), Pd1–N2 2.068(3), Pd1–Cl1 2.3898(12), C1–Pd1–
Cl1 177.89(13), N1–Pd1–N2 158.06(12).
The reaction of the N,C,O-chelated organogold(I) com-
pound 3 with [PdCl2(CH3CN)2] did not afford any isolable
N,C,O-chelated organopalladium(II) compounds, although
monitoring of the reaction by 31P NMR spectroscopy
clearly proved that the starting material 3 was consumed
and [AuCl(PPh3)] emerged in the reaction mixture. Never-
1
theless, the H NMR spectrum suggested the formation of
a rather complicated mixture of products, which was not
separable. This result could be ascribed to the presence of
a weakly coordinating oxygen functionality, which is, most
Figure 7. ORTEP diagram of compound 9 with thermal displace-
ment parameters at 30% probability, hydrogen atoms were omitted
for clarity. Selected distances [Å] and angles [°]: Pt1–C1 2.007(4),
Pt1–N1 2.150(3), Pt1–P1 2.2307(9), Pt1–Cl1 2.3997(9), Pt1–
probably, not able to sufficiently stabilize the incipient prod- O1 3.778(3), C1–Pt1–Cl1 165.12(12), N1–Pt1–P1 161.53(14).
uct.
The 31P NMR spectrum of the reaction mixture after
treatment of 3 with [PtCl2(Et2S)2] revealed two signals at δ
The potentially terdentate N,C,O pincer-type ligand is
= 32.7 ppm for [AuCl(PPh3)] together with a new signal at coordinated to the central platinum atom only in a N,C
1
δ = 11.4 ppm with JPt,P = 4271 Hz, and from this reaction bidentate fashion and the oxygen-containing ligand arm re-
mixture compound L3PtCl(PPh3) (9) was isolated in low mains pendant. The coordination sphere of the platinum
1
yield. The JPt,P value of 4271 Hz in 9 is a typical value atom is completed by the chlorine atom and triphenylphos-
comparable to those found in related complexes.[19] The tri- phane donor. In the square planar array, the N1, P1 and
phenylphosphane present in the structure of 9 must be C1, Cl1 are placed mutually in trans positions. The oxygen
moved from the incipient [AuCl(PPh3)] to the platinum cen- atom-containing donor arm is orientated above the plati-
tre, which caused the low yield of the reaction. This pre- num atom, which most probably causes a slight defor-
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mation of the bonding angles C1–Pt1–Cl1 165.12(12) and
N1–Pt1–P1 161.53(14)° from the ideal value of 180°. How-
ever, the oxygen donor atom remains outside the primary
coordination sphere of the central platinum atom as dem-
onstrated by the bond length Pt1–O1 3.778(3) Å. This ob-
servation seems to be a bit more questionable in solution.
The 13C NMR spectra of this compound showed the cou-
pling between the carbon atom of the CH2N groups and
the platinum atom as well as the phosphorus atom from the
Conclusions
In conclusion, four novel organogold(I) compounds 1–4
were prepared, characterized and their transmetalation po-
tential was tested in the reactions with [PdCl2(CH3CN)2]
and [PtCl2(Et2S)2]. It turned out that compounds 1 and 2
are useful starting materials and transmetalation using
them proceeded smoothly regardless of whether a poten-
tially bidentate (L1) or terdentate (L2) ligand was employed.
On the contrary, it is evident that using precursors contain-
ing oxygen-donor functionalities 3 and 4 (L3 and L4) is not
possible for the clean synthesis of palladium(II) complexes
and only more kinetically stable platinum(II) complexes
were isolated. It is worth mentioning that in both cases the
oxygen atoms remain noncoordinated in the product and
stabilization by additional ancillary soft ligands such as
Et2S or Ph3P is necessary. It is most probably a consequence
of highly unfavourable intramolecular OǞPd(Pt) interac-
tions, which lead to the decomposition of the products in
the case of the palladium compounds. Of importance is also
the further investigation of reactions of compounds 1 and
3 with other transition-metal halides, which is currently un-
derway in our labs.
2
3
Ph3P moiety [with the values of JPt,C = 53 Hz and JP,C
=
4 Hz], interestingly, rather similar coupling was also ob-
3
served for the CH2O groups (2JPt,C = 54 Hz, JP,C = 6 Hz,
see also Supporting Information). This observation indi-
cates that the OǞPt interaction in solution for compound
9 is most probably not negligible. Interestingly, it has been
recently demonstrated that in the closely related palladi-
um(II) P,C,O pincer-type compounds the oxygen function-
ality is involved in an intramolecular OǞPd coordina-
tion.[20] In this regard, the concept of hemilabile coordina-
tion[21] of the oxygen donor group taking place in the case
of 9 may be considered.
Finally, the reaction between compound 4 and [PdCl2-
(CH3CN)2] did not result in any isolable palladium(II) com-
pounds and the situation and reaction mixture closely re-
sembles this described in the case of the reaction of 3 and
[PdCl2(CH3CN)2] vide supra. Nevertheless, the reaction be-
tween 4 and [PtCl2(Et2S)2] proceeded smoothly and quanti-
Experimental Section
General Procedures: All air and moisture sensitive manipulations
were carried out under an argon atmosphere using standard
Schlenk tube techniques. All solvents were dried by standard pro-
1
tatively, according to the H NMR and 31P NMR spectra,
to produce compound L4PtCl(Et2S)2 (10), which was iso-
lated in 79% yield after workup (Scheme 6). Compound 10
displayed satisfactory elemental analysis and ESI mass
spectra, where ions [M – Cl]+, [M – Cl – Et2S]+, [M – Cl-
2Et2S]+ or [M – Cl – Et2S – HCOH]+ were observed in the
cedures and distilled prior to use. H NMR and 13C NMR spectra
1
were recorded with a Bruker 400 spectrometer using a 5-mm tun-
able broadband probe. Appropriate chemical shifts in the 1H NMR
and 13C NMR spectra were related to the residual signals of the
solvent [C6D6: δ(1H) = 7.16 ppm, δ(13C) = 128.39 ppm]. The start-
ing ligands L1–4 were prepared according to literature pro-
cedures.[5c,13,14,22] All other chemicals were purchased from com-
mercial suppliers and were used as delivered. Positive-ion electro-
spray ionization (ESI) mass spectra were measured with an Esquire
3000 ion trap analyzer (Bruker Daltonics, Bremen, Germany) in
the range m/z = 50–1200. Samples were dissolved in acetonitrile
and analyzed by direct infusion at a flow rate of 5 μL/min. The ion
source temperature was 300 °C, the flow rate and the pressure of
nitrogen were 4 L/min and 10 psi, respectively.
1
positive-ion full-scan mass spectrum. The H NMR spec-
trum contained, besides signals of the ligand L4, signals at
δ = 0.98 and 2.61 ppm, corresponding to the coordinated
S(CH2CH3)2 molecules. The 13C NMR spectra proved the
presence of two trans-coordinated diethyl sulfides by the
observation of the signals at δ = 13.2 and 29.2 ppm. Al-
though many attempts were made to determine the solid-
state structure of 10 using single-crystal X-ray diffraction
analysis, the molecular structure could not be refined com-
pletely because of an extensive disorder of the backbone of
the ligand.
[o-C6H4(CH=NC6H3iPr2-2,6)]AuPPh3
(1): nBuLi
(2.5 mL,
4.1 mmol, 1.6 m solution in hexane) was added to a solution of
[o-C6H4(CH=NC6H3iPr2-2,6)]Br (1.40 g, 4.1 mmol) in diethyl ether
(20 mL) at –70 °C and stirred for 30 min at this temperature. A
suspension of [AuCl(PPh3)] (2.01 g, 4.1 mmol) in diethyl ether
(30 mL), precooled to –70 °C, was added to the resulting yellow-
orange suspension of the lithium compound. The obtained orange
mixture was allowed to reach room temp. and stirred overnight.
The insoluble material was filtered off in the air and the filtrate
volume was reduced to ca. one third. Hexane (10 mL) was added
to this solution and the mixture was left standing for crystallization
at 5 °C for several days. The obtained air-stable colourless crystals
of compound 1 were decanted from the solution and dried in
vacuo. Compound 1 was stable in air for a long time (several
months); yield 2.50 g, 85%; m.p. 82 °C. Positive-ion ESI-MS: m/z
(%) = 1182 [M + AuPPh3]+, 762 [M + K]+, 746 [M + Na]+, 724
1
[M + H]+, 100. H NMR (400 MHz, C6D6, 25 °C): δ = 1.09 [d, 12
Scheme 6. Preparation of 10.
H, CH(CH3)2], 3.38 [sept, 2 H, CH(CH3)2], 6.88 (m, 6 H, m-H-
6
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Various Chelated Organogold(I) Compounds
PPh3), 6.97 (m, 3 H, p-H-PPh3), 7.16 (m, 3 H, C6H3iPr2-2,6), 7.27
(d, 2 H, C6H4), 7.45 (m, 6 H, o-H-PPh3), 8.20 (d, 1 H, C6H4), 8.33
(d, 1 H, C6H4), 9.13 (s, 1 H, CH=N) ppm. 13C NMR (100.61 MHz,
C6D6, 25 °C): δ = 24.1 [s, CH(CH3)2], 28.8 [s, CH(CH3)2], 123.6 (s,
Ar-C), 124.1 (s, Ar-C), 126.5 (s, Ar-C), 128.9 (s, Ar-C), 129.4 (d,
3JP,C = 11 Hz, PPh3-C), 130.8 (s, Ar-C), 131.3 (s, PPh3-C), 131.8
NMR (161.97 MHz, C6D6, 25 °C): δ = 44.9 ppm. C29H31AuNOP
(637.51): calcd. C 54.6, H 4.9; found C 54.8, H 5.1.
[o,o-C6H3(CH2OMe)2]AuPPh3 (4): nBuLi (1.9 mL, 3.1 mmol, 1.6 m
solution in hexane) was added to
a
solution of [o,o-
C6H3(CH2OMe)2]Br (749 mg, 3.1 mmol) in diethyl ether (20 mL)
at –78 °C and stirred for 3 h. A suspension of [AuCl(PPh3)] (1.51 g,
3.1 mmol) in diethyl ether (20 mL) precooled to –70 °C was added
to the resulting suspension of the lithium compound. The obtained
yellow mixture was allowed to reach room temperature and stirred
for an additional 2 h. The insoluble material was filtered off in air,
then washed with diethyl ether and the filtrate volume was reduced
to ca. half. Hexane (5 mL) was added to this solution and the mix-
ture was left for crystallization at –30 °C for several days. Obtained
colourless crystals of compound 4 were decanted from solution and
dried in vacuo. Compound 4 was stored under an argon atmo-
sphere and very slow decomposition to a black material was no-
ticed after several months at 5 °C; yield 965 mg, 51%; m.p. 118 °C.
Positive-ion ESI-MS: m/z (%) = 1083 [M + AuPPh3]+, 1053 [M +
AuPPh3 – HCOH]+, 663 [M + K]+, 647 [M + Na]+, 100, 625 [M +
1
(d, JP,C = 48 Hz, PPh3-C), 134.9 (d, 2JP,C = 14 Hz, PPh3-C), 138.7
(s, Ar-C), 141.5 (s, Ar-C), 145.7 (s, Ar-C), 151.9 (s, Ar-C), 169.0 (s,
CH=N) ppm, (Ar-ipso-C) not observed. 31P NMR (161.97 MHz,
C6D6, 25 °C): δ = 44.1 ppm. C37H37AuNP (723.65): calcd. C 61.4,
H 5.2; found C 61.5, H 5.4.
{o,o-C6H3[C(Me)=NC6H3Me2-2,6]2}AuPPh3 (2): nBuLi (1.5 mL,
2.4 mmol, 1.6 m solution in hexane) was added to a solution of
[o,o-C6H3(C(Me)=NC6H3Me2-2,6)2]Br (522 mg, 1.2 mmol) in di-
ethyl ether (20 mL) at –70 °C and stirred for 30 min at this tempera-
ture. A suspension of [AuCl(PPh3)] (578 mg, 1.2 mmol) in diethyl
ether (30 mL) precooled to –70 °C was added to the resulting
orange suspension of the lithium compound. The obtained orange
mixture was allowed to reach room temp. and stirred for an ad-
ditional 48 h. The insoluble material was filtered off and the filtrate
volume was reduced to ca. half. Hexane (20 mL) was added into
this solution and the mixture was left for crystallization at –30 °C
for several days. The obtained honey-yellow crystals of compound
2 were decanted from solution and dried in vacuo. Compound 2 is
stable in air for a long time (several months); yield 815 mg, 85%;
m.p. 208 °C. Positive-ion ESI-MS: m/z (%) = 865 [M + K]+, 849
[M + Na]+, 827 [M + H]+, 100. 1H NMR (400 MHz, C6D6, 25 °C):
δ = 2.05 [s, 12 H, C6H3(CH3)2-2,6], 2.20 [s, 6 H, C(CH3)=N], 6.91
[m, 15 H, m,p-H-PPh3 and C6H3(CH3)2-2,6], 7.30 (t, 1 H, C6H4-
H4), 7.34 (m, 6 H, o-H-PPh3), 7.94 (d, 1 H, C6H4-H3,5) ppm. 13C
NMR (100.61 MHz, C6D6, 25 °C): δ = 19.0 [s, C6H3(CH3)2-2,6],
22.0 [s, C(CH3)=N], 122.8 (s, Ar-C), 125.7 (s, Ar-C), 126.8 (s, Ar-
C), 128.5 (s, Ar-C), 129.3 (d, 3JP,C = 11 Hz, PPh3-C), 131.1 (d, 4JP,C
1
H]+. H NMR (400 MHz, C6D6, 25 °C): δ = 3.36 (s, 6 H, OCH3),
5.10 (s, 2 H, OCH2), 7.00 (m, 9 H, m,p-H-PPh3), 7.37 (t, 1 H, C6H4-
H4), 7.55 (m, 6 H, o-H-PPh3), 7.75 (d, 2 H, C6H4) ppm. 13C NMR
(100.61 MHz, C6D6, 25 °C): δ = 57.9 (s, OCH3), 80.4 (s, OCH2),
3
126.4 (s, Ar-C), 127.5 (s, Ar-C), 129.5 (d, JP,C = 11 Hz, PPh3-C),
4
1
131.5 (d, JP,C = 2 Hz, PPh3-C), 132.1 (d, JP,C = 49 Hz, PPh3-C),
2
134.9 (d, JP,C = 14 Hz, PPh3-C), 147.6 (s, Ar-C) ppm, (Ar-ipso-C)
not observed. 31P NMR (161.97 MHz, C6D6, 25 °C): δ = 44.4 ppm.
C28H28AuO2P (624.27): calcd. C 53.9, H 4.5; found C 53.7, H 4.7.
{[o-C6H4(CH=NC6H3iPr2-2,6)]PdCl}2 (5):
A
solution of
[PdCl2(CH3CN)2] (66 mg, 0.25 mmol) in acetonitrile (15 mL) was
added to a stirred solution of 1 (183 mg, 0.25 mmol) in benzene
(20 mL) in a small round-bottom flask. The resulting mixture was
heated to 70 °C for 2 h. The obtained yellow-green solution was
evaporated in vacuo. The reaction mixture was characterized by
1H NMR and 31P NMR spectroscopy proving that the reaction
proceeded almost quantitatively (see Results and Discussion). The
residue was extracted by a mixture of dichloromethane/hexane
(10:1) and the traces of insoluble material were filtered off. The
filtrate was left to crystallize by slow evaporation at room temp.
The obtained ginger crystals of 5 were decanted, washed with hex-
ane and dried in vacuo; yield 31 mg, 30%; m.p. 205 °C (dec.). Posi-
tive-ion ESI-MS: m/z (%) = 411 [M – Cl + CH3CN]+, 100, 388
1
2
= 5 Hz, PPh3-C), 132.5 (d, JP,C = 49 Hz, PPh3-C), 134.8 (d, JP,C
= 15 Hz, PPh3-C), 151.2 (s, Ar-C), 151.4 (s, Ar-C), 172.6 (s, Ar-C),
172.7 (s, CH=N) ppm. 31P NMR (161.97 MHz, C6D6, 25 °C): δ =
41.9 ppm. C44H42AuN2P (826.78): calcd. C 63.9, H 5.1; found C
64.3, H 5.3.
[o,oЈ-C6H3(CH2NMe2)(CH2OMe)]AuPPh3 (3): nBuLi (2.5 mL,
4.0 mmol, 1.6 m solution in hexane) was added to a solution of
o,oЈ-C6H4(CH2NMe2)(CH2OMe) (708 mg, 4.0 mmol) in hexane
(20 mL) at room temp. and stirred for 2 h. The orange solution of
the lithium compound was added to a suspension of [AuCl(PPh3)]
(1.95 g, 4.0 mmol) in diethyl ether (30 mL) and precooled to
–70 °C. The obtained creamy mixture was allowed to reach room
temperature and stirred for an additional 24 h. The resulting sus-
pension was filtered in the air over Celite. The insoluble material
was washed with diethyl ether and the filtrate was left to slowly
evaporate at room temp. giving colourless crystals within several
hours. The obtained air stable colourless crystals of compound 3
were collected by filtration and washed by hexane and dried in
vacuo. Compound 3 is stable in air for a long time (several months);
yield 1.41 g, 56%; m.p. 124 °C. Positive-ion ESI-MS: m/z (%) = 676
[M + K]+, 660 [M + Na]+, 638 [M + H]+, 100, 178 [L]+. 1H NMR
(400 MHz, C6D6, 25 °C): δ = 2.28 [s, 6 H, N(CH3)2], 3.38 (s, 3 H,
1
[M – Cl + H2O]+. H NMR (400 MHz, C6D6, 25 °C): δ = 0.96 [d,
6 H, CH(CH3)2], 1.39 [d, 6 H, CH(CH3)2], 3.58 [sept, 2 H,
CH(CH3)2], 6.64 (dd, C6H4), 6.70 (dd, C6H4), 6.75 (dd, C6H4), 7.07
(m, 3 H, C6H3iPr2-2,6), 7.12 (s, 1 H, CH=N), 7.54 (d, 1 H,
C6H4) ppm. Other NMR spectroscopic data in CDCl3 were consis-
tent with those published.[16] C38H44Cl2N2Pd2 (812.5): calcd. C
56.2, H 5.5; found C 56.5, H 5.7.
[o-C6H4(CH=NC6H3iPr2-2,6)]PtCl(Et2S) (6):
A
solution of
[PtCl2(Et2S)2] (129 mg, 0.29 mmol) in benzene (15 mL) was added
to a stirred solution of 1 (209 mg, 0.29 mmol) in benzene (20 mL)
in a small round-bottom flask. The resulting mixture was heated
to 70 °C for 2 h. The obtained orange solution was evaporated in
OCH3), 3.96 (s, 2 H, NCH2), 5.15 (s, 2 H, OCH2), 7.03 (m, 9 H, vacuo. The reaction mixture was characterized by 1H NMR and
m,p-H-PPh3), 7.35 (dd, 1 H, C6H4), 7.60 (m, 6 H, o-H-PPh3), 7.65 31P NMR spectroscopy proving that the reaction proceeded quanti-
(d, 1 H, C6H4), 7.76 (d, 1 H, C6H4) ppm. 13C NMR (100.61 MHz, tatively (see Results and Discussion). The residue was extracted by
C6D6, 25 °C): δ = 46.4 [s, N(CH3)2], 58.0 (s, OCH3), 71.0 (s, NCH2),
80.5 (s, OCH2), 126.1 (s, Ar-C), 126.7 (s, Ar-C), 128.6 (s, Ar-C),
diethyl ether and the insoluble material {[AuCl(PPh3)]} was filtered
off. The filtrate volume was reduced to ca. half, and a small amount
of hexane was added and the resulting mixture was left to crys-
tallize at 5 °C. Obtained orange crystals of 6 were decanted from
the solution and dried in vacuo; yield 100 mg, 78%; m.p. 200 °C
3
4
129.5 (d, JP,C = 11 Hz, PPh3-C), 131.5 (d, JP,C = 2 Hz, PPh3-C),
2
132.3 (d, 1JP,C = 48 Hz, PPh3-C), 134.9 (d, JP,C = 14 Hz, PPh3-C),
147.6 (s, Ar-C), 148.7 (s, Ar-C) ppm, (Ar-ipso-C) not observed. 31
P
Eur. J. Inorg. Chem. 0000, 0–0
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Pages: 11
L. Dostál et al.
proceeded almost quantitatively (see Results and Discussion). The
FULL PAPER
(dec.). Positive-ion ESI-MS: m/z (%) = 623 [M + K]+, 607 [M +
Na]+, 549 [M – Cl]+, 100. H NMR (400 MHz, C6D6, 25 °C): δ = residue was washed by diethyl ether and the insoluble material was
1
1.09 [m, 12 H, overlap of CH(CH3)2 and S(CH2CH3)2], 1.56 [d, 6
filtered. The insoluble material was dried in vacuo and extracted
H, CH(CH3)2], 2.30 [m, 2 H, S(CH2CH3)2], 3.17 [m, 2 H, by benzene. The extract was left to crystallize by slow evaporation
S(CH2CH3)2], 3.58 [sept, 2 H, CH(CH3)2], 6.94 (m, 2 H, C6H4), at room temp. The obtained yellow crystals of 9 were decanted
7.00 (dd, 1 H, C6H4), 7.17 (m, 3 H, C6H3iPr2-2,6), 7.63 (s, 3JPt,H
=
from solution and dried in vacuo; yield 241 mg, 69%; m.p. 180 °C
3
1
119 Hz, 1 H, CH=N), 7.90 (d, JPt,H = 45 Hz, 1 H, C6H4) ppm.
(dec.). Positive-ion ESI-MS: m/z = 635 [M – Cl]+, 100. H NMR
2
13C NMR (100.61 MHz, C6D6, 25 °C): δ = 13.3 [s, JPt,C = 32 Hz, (400 MHz, C6D6, 25 °C): δ = 2.44 [s, 6 H, N(CH3)2], 3.07 (s, 3 H,
3
S(CH2CH3)2], 23.7 [s, CH(CH3)2], 24.8 [s, CH(CH3)2], 28.7 [s, OCH3), 3.59 (s, JPt,H = 31 Hz, 2 H, NCH2), 3.92 (s, 2 H, OCH2),
1
CH(CH3)2], 32.1 [s, JPt,C = 20 Hz, S(CH2CH3)2], 123.5, 123.8,
6.98 (m, 9 H, m,p-H-PPh3), 7.05 (dd, 1 H, C6H4), 7.10 (m, 2 H,
2
130.0, 132.0, 133.4, 142.5, 145.3, 147.0, 148.7, 180.8 (s, JPt,C
=
C6H4), 7.88 (m, 6 H, o-H-PPh3) ppm. 13C NMR (100.61 MHz,
2
91 Hz, CH=N) ppm, (Ar-ipso-C) not observed. C23H32ClNPtS
(585.13): calcd. C 47.2, H 5.5; found C 47.5, H 5.7.
C6D6, 25 °C): δ = 50.3 [s, N(CH3)2], 57.5 (s, OCH3), 75.7 (d, JPt,C
3
2
3
= 53, JP,C = 4 Hz, NCH2), 79.7 (d, JPt,C = 54, JP,C = 6 Hz,
OCH2), 121.7 (s, Ar-C), 124.5 (s, Ar-C), 127.5 (s, Ar-C), 128.3 (d,
{o,o-C6H3[C(Me)=NC6H3Me2-2,6]2}PdCl (7):
A
solution of
3JP,C = 11 Hz, PPh3-C), 130.8 (s, JP,C = 2 Hz, PPh3-C), 135.9 (d,
4
[PdCl2(CH3CN)2] (35 mg, 0.14 mmol) in acetonitrile (15 mL) was
added to a stirred solution of 2 (111 mg, 0.14 mmol) in benzene
(20 mL) in a small round-bottom flask. The resulting mixture was
heated to 70 °C for 4 h. The obtained dirty-yellow solution was
evaporated in vacuo. The reaction mixture was characterized by
1H NMR and 31P NMR spectroscopy proving that the reaction
proceeded quantitatively (see Results and Discussion). The residue
was extracted by a mixture of dichloromethane/hexane (10:1) and
traces of insoluble material were filtered off. The filtrate was left to
crystallize by slow evaporation at room temp. The obtained pale-
yellow crystals of 7 were decanted from solution and dried in
vacuo; yield 38 mg, 56%; m.p. 294 °C (dec.). Positive-ion ESI-MS:
m/z (%) = 985 [2M – 2Cl + K]+, 547 [M + K]+, 491 [M – Cl +
2JP,C = 11 Hz, PPh3-C), 143.6 (s, Ar-C), 146.0 (d, JP,C = 7 Hz,
1
PPh3-C) 147.0 (Ar-C) ppm, (Ar-ipso-C) not observed. 31P NMR
(161.97 MHz, C6D6, 25 °C): δ = 11.4 (1JPt,P = 4271 Hz) ppm.
C29H31ClNOPPt (671.09): calcd. C 51.9, H 4.7; found C 51.6, H
5.0.
[o,o-C6H3(CH2OMe)2]PtCl(Et2S)2 (10):
A solution of [PtCl2-
(Et2S)2] (216 mg, 0.48 mmol) in benzene (15 mL) was added to a
stirred solution of 4 (302 mg, 0.48 mmol) in benzene (20 mL) in a
small round-bottom flask. The resulting mixture was heated to
70 °C for 2 h. The obtained pale-orange suspension was evaporated
1
in vacuo The reaction mixture was characterized by H NMR and
31P NMR spectroscopy proving that the reaction proceeded quanti-
tatively (see Results and Discussion). The residue was extracted by
diethyl ether and the insoluble material {[AuCl(PPh3)]} was filtered
off. The filtrate volume was reduced to half, then a small amount
of hexane was added and the resulting solution was left to crys-
tallize at 5 °C. The obtained yellow crystals of 10 were decanted
from solution and dried in vacuo; yield 220 mg, 79%; m.p. 88 °C.
Positive-ion ESI-MS: m/z (%) = 540 [M – Cl]+, 510 [M – Cl –
HCOH]+, 450 [M – Cl – Et2S]+, 100, 420 [M – Cl – Et2S –
HCOH]+, 360 [M – Cl – 2Et2S]+. 1H NMR (400 MHz, C6D6,
25 °C): δ = 0.98 [t, 6 H, S(CH2CH3)2], 2.61 [m, 4 H, S(CH2-
CH3)2], 3.36 [s, 6 H, O(CH3)], 5.01 [s, 2 H, O(CH2)], 7.08 (t, 1 H,
C6H4-H4), 7.37 (d, 2 H, C6H4) ppm. 13C NMR (100.61 MHz,
1
H2O]+, 473 [M – Cl]+, 100. H NMR (400 MHz, C6D6, 25 °C): δ
= 1.47 [s, 6 H, C(CH3)=N], 2.21 [s, 12 H, C6H3(CH3)2-2,6], 6.86
(m, 3 H, C6H4), 6.94 [s, 6 H, C6H3(CH3)2-2,6] ppm. 13C NMR
(100.61 MHz, C6D6, 25 °C): δ = 15.9 [s, C(CH3)=N], 19.2 [s,
C6H3(CH3)2-2,6], 123.0, 127.0, 128.7, 130.4, 145.7, 145.8, 184.1,
186.0 (s, CH=N and Ar-C) ppm. C26H27ClN2Pd (509.37): calcd. C
61.3, H 5.3; found C 61.5, H 5.4.
{o,o-C6H3[C(Me)=NC6H3Me2-2,6]2}PtCl (8):
A
solution of
[PtCl2(Et2S)2] (60 mg, 0.14 mmol) in benzene (15 mL) was added
to a stirred solution of 2 (111 mg, 0.14 mmol) in benzene (20 mL)
in a small round-bottom flask. The resulting mixture was heated
to 70 °C for 24 h. The obtained honey-coloured solution was evap-
orated in vacuo. The reaction mixture was characterized by 1H
NMR and 31P NMR spectroscopy proving that the reaction pro-
ceeded quantitatively (see Results and Discussion). The residue was
extracted by a mixture of dichloromethane/hexane (10:1) and the
insoluble material was filtered off. The filtrate was left to crystallize
by free evaporation at room temp. The obtained orange crystals of
8 were decanted from solution and dried in vacuo; yield 49 mg,
61%; m.p. 205 °C (dec.). Positive-ion ESI-MS: m/z (%) = 580 [M –
Cl + H2O]+, 100, 562 [M – Cl]+. 1H NMR (400 MHz, C6D6, 25 °C):
2
C6D6, 25 °C): δ = 13.2 [s, JPt,C = 45 Hz, S(CH2CH3)2], 29.2 [s,
S(CH2CH3)2], 58.8 (s, OCH3), 79.5 (s, OCH2), 124.8, 127.8, 143.3
(s, Ar-C) ppm, (Ar-ipso-C) signal not observed. C18H33ClO2PtS2
(576.1): calcd. C 37.5, H 5.8; found C 37.7, H 5.7.
X-ray Crystallography: The suitable single crystals of the studied
compounds were mounted on glass fibres with an oil and measured
with a four-circle diffractometer KappaCCD with CCD area detec-
tor by monochromatized Mo-Kα radiation (λ = 0.71073 Å) at
150(1) K. The numerical[23] absorption corrections from the crystal
shapes were applied for all crystals. The structures were solved by
the direct method (SIR92)[24] and refined by a full-matrix least-
squares procedure based on F2 (SHELXL97).[25] Hydrogen atoms
were fixed into idealized positions (riding model) and assigned tem-
perature factors Hiso(H) = 1.2Ueq (pivot atom) or of 1.5Ueq for the
methyl moiety with C–H bond lengths of 0.96, 0.97 and 0.93 Å
4
δ = 1.48 [s, JPt,H = 8 Hz, 6 H, C(CH3)=N], 2.14 [s, 12 H,
C6H3(CH3)2-2,6], 6.94 (m, 3 H, C6H4), 7.08 [m, 6 H, C6H3(CH3)2-
2
2,6] ppm. 13C NMR (100.61 MHz, C6D6, 25 °C): δ = 16.1 [s, JPt,C
= 58 Hz, C(CH3)=N], 18.6 [s, C6H3(CH3)2-2,6], 121.1, 127.4, 128.5,
128.7, 131.2, 143.6, 145.9, 176.2, 186.1 (s, CH=N and Ar-C) ppm.
C26H27ClN2Pt (598.06): calcd. C 52.2, H 4.6; found C 52.5, H 4.9.
[o,oЈ-C6H3(CH2NMe2)(CH2OMe)]PtPPh3 (9):
A solution of for methyl, methylene and hydrogen atoms in the aromatic ring,
[PtCl2(Et2S)2] (233 mg, 0.52 mmol) in benzene (15 mL) was added
to a stirred solution of 3 (333 mg, 0.52 mmol) in benzene (20 mL)
respectively. The final difference maps displayed no peaks of chemi-
cal significance as the highest peaks and holes are in close vicinity
(ca. 1 Å) of heavy atoms. The crystal structure of 9 was determined
at room temperature because the single crystal of this compound
undergoes a phase transformation at 150 K. Some of the carbon
atoms of the solvent (toluene) in 2 were disordered but attempts
made to split these gave no better data set.
in
a small round-bottom flask. Finally triphenylphosphane
(137 mg, 0.52 mmol) was added. The resulting mixture was heated
to 70 °C for 2 h. The obtained pale-orange suspension was evapo-
rated in vacuo. The reaction mixture was characterized by the help
1
of H NMR and 31P NMR spectroscopy proving that the reaction
8
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Eur. J. Inorg. Chem. 0000, 0–0

Job/Unit: I20152
/KAP1
Date: 02-04-12 10:46:02
Pages: 11
Various Chelated Organogold(I) Compounds
CCDC-863055 (for 4), -863056 (for 2), -863057 (for 3), -863058 (for
1), -863059 (for 6), -863060 (for 9), -863061 (for 7), -863062 (for 5)
contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_requ-
est/cif.
[1]
a) M. Albrecht, G. van Koten, Angew. Chem. 2001, 113, 3866;
Angew. Chem. Int. Ed. 2001, 40, 3750–3781; b) M. E.
van der Boom, D. Milstein, Chem. Rev. 2003, 103, 1759–1792;
c) D. Morales–Morales, C. M. Jensen, The chemistry of pincer
compounds, Elsevier, Amsterdam, 2007; d) C. Gunanathan, D.
Milstein, Acc. Chem. Res. 2011, 44, 588–602; e) S. Schneider,
J. Meiners, B. Askevold, Eur. J. Inorg. Chem. 2012, 412–429; f)
J. I. van der Vlugt, J. N. H. Reek, Angew. Chem. 2009, 121,
8990; Angew. Chem. Int. Ed. 2009, 48, 8832–8846.
For early examples see: a) C. J. Moulton, B. L. Shaw, J. Chem.
Soc., Dalton Trans. 1976, 1020–1024; b) G. van Koten, K.
Timmer, J. G. Noltes, A. L. Spek, J. Chem. Soc., Chem. Com-
mun. 1978, 250–252; c) C. S. Creaser, W. C. Kaska, Inorg. Chim.
Acta 1978, 30, L325–L326; G. van Koten, Pure Appl. Chem.
1989, 61, 1681.
Crystallographic Data for 1: C37H37AuNP, Mr = 723.61 g/mol,
monoclinic, P21,
a = 13.4191(3) Å, b = 6.8730(4) Å, c =
16.9638(10) Å, β = 90.329(4)°, V = 1564.54(13) Å3, Z = 2, T =
150(1) K, 7491 total reflections, 5064 independent [Rint = 0.061, R1
(obsd. data) = 0.058, wR2 (all data) = 0.148].
[2]
[3]
Crystallographic Data for 2: C44H42AuN2P·(C7H8), Mr = 918.87 g/
¯
mol, triclinic, P1, a = 11.9179(9) Å, b = 14.6980(9) Å, c =
14.8970(4) Å, α = 113.629(5)°, β = 96.618(4)°, γ = 111.699(6)°, V
= 2112.3(2) Å3, Z = 2, T = 150(1) K, 41956 total reflections, 9653
independent [Rint = 0.031, R1 (obsd. data) = 0.027, wR2 (all data)
= 0.056].
For example see Group 13: a) A. H. Cowley, F. P. Gabbäi,
D. A. Atwood, J. Am. Chem. Soc. 1994, 116, 1559–1560; b)
A. H. Cowley, R. A. Jones, M. A. Mardones, J. Ruiz, J. L. At-
wood, S. G. Bott, Angew. Chem. 1990, 102, 1169; Angew. Chem.
Int. Ed. Engl. 1990, 102, 1150–1151; c) L. Dostál, R. Jambor,
Crystallographic Data for 3: C29H31AuNOP, Mr = 637.48 g/mol,
monoclinic, P21/c, a = 14.9700(12) Å, b = 8.5400(5) Å, c =
22.7451(15) Å, β = 116.593(6)°, V = 2600.2(3) Å3, Z = 4, T =
150(2) K, 21703 total reflections, 5949 independent [Rint = 0.044,
R1 (obsd. data) = 0.034, wR2 (all data) = 0.062].
A. Ru˚zicˇka, R. Jirásko, I. Císarˇová, J. Holecˇek, J. Organomet.
ˇ
Chem. 2006, 691, 35–44; Group 14: d) R. Jambor, B. Kasˇná,
K. N. Kirschner, M. Schürmann, K. Jurkschat, Angew. Chem.
2008, 120, 1674; Angew. Chem. Int. Ed. 2008, 47, 1650–1653;
e) M. Mehring, I. Vrasidas, D. Horn, M. Schürmann, K. Jurk-
schat, Organometallics 2001, 20, 4647–4653; f) M. Henn, M.
Schürmann, B. Mahieu, P. Zanello, A. Cinquantini, K. Jurk-
schat, J. Organomet. Chem. 2006, 691, 1560–1572; g) M. Bou-
Crystallographic Data for 4: C28H28AuO2P, Mr = 624.44 g/mol,
monoclinic, P21/c, a = 10.9530(8) Å, b = 8.2310(3) Å, c =
28.9221(15) Å, β = 107.298(6)°, V = 2489.5(3) Å3, Z = 4, T =
150(1) K, 17305 total reflections, 5668 independent [Rint = 0.041,
R1 (obsd. data) = 0.043, wR2 (all data) = 0.081].
sˇka, L. Dostál, F. de Proft, A. Ru˚zicˇka, A. Lycˇka, R. Jambor,
ˇ
Chem. Eur. J. 2011, 17, 455–459; h) E. Bonnefille, S. Mazières,
C. Bibal, N. Saffon, H. Gornitzka, C. Couret, Eur. J. Inorg.
Chem. 2008, 4242–4424; Group 15: i) L. Balázs, H. J. Breunig,
E. Lork, A. P. Soran, C. Silvestru, Inorg. Chem. 2006, 45, 2341–
Crystallographic data for 5: C38H44Cl2N2Pd2, Mr = 812.45 g/mol,
monoclinic, P21/c, a = 11.0470(2) Å, b = 10.2780(5) Å, c =
16.5011(11) Å, β = 105.359(3)°, V = 1806.64(15) Å3, Z = 2, T =
150(1) K, 13857 total reflections, 4027 independent [Rint = 0.025,
R1 (obsd. data) = 0.022, wR2 (all data) = 0.049].
2346; j) L. Dostál, R. Jambor, A. Ru˚zicˇka, J. Holecˇek, Organo-
ˇ
metallics 2008, 27, 2169–2171; k) L. Dostál, R. Jambor, A. Ru˚-
ˇ
zicˇka, M. Erben, R. Jirásko, Z. Cernosˇková, J. Holecˇek, Orga-
ˇ
nometallics 2009, 28, 2633–2636; l) K. Peveling, M. Schur-
mann, S. Herres-Pawlis, C. Silvestru, K. Jurkschat, Organome-
tallics 2011, 30, 5181–5187; m) I. J. Casely, J. W. Ziller, B. J.
Mincher, W. J. Evans, Inorg. Chem. 2011, 50, 1513–1520; n) R.
Thirumoorthi, T. Chivers, I. Vargas-Baca, Dalton Trans. 2011,
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2012, DOI: 10.1021/ic202213x.
a) A. D. Ryabov, Chem. Rev. 1990, 90, 403–424; b) P. Steenwin-
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762.
Crystallographic Data for 6: C23H32ClNPtS, Mr = 585.10 g/mol,
orthorhombic, P212121, a = 11.1509(3) Å, b = 14.0480(10) Å, c =
15.1001(14) Å, V = 2365.4(3) Å3, Z = 4, T = 150(1) K, 21005 total
reflections, 5415 independent [Rint = 0.054, R1 (obsd. data) = 0.028,
wR2 (all data) = 0.060].
[4]
[5]
Crystallographic Data for 7: C26H27ClN2Pd, Mr = 509.35 g/mol,
orthorhombic, P212121, a = 12.7667(10) Å, b = 12.7910(8) Å, c =
14.3100(8) Å, V = 2336.8(3) Å3, Z = 4, T = 150(1) K, 10469 total
reflections, 5063 independent [Rint = 0.044, R1 (obsd. data) = 0.035,
wR2 (all data) = 0.066].
a) D. M. Grove, G. van Koten, H. J. C. Ubbels, R. Zoet, A. L.
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Grove, K. Goublitz, M. C. Zoutberg, C. H. Stam, W. J. J.
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Stol, D. J. M. Snelders, M. D. Godbole, R. W. A. Havenith, D.
Haddleton, G. Clarkson, M. Lutz, A. L. Spek, G. P. M.
van Klink, G. van Koten, Organometallics 2007, 26, 3985–3994.
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Organometallics 2000, 19, 4468–4476; b) M. Albrecht, P. Dani,
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F. Maassarani, M. F. Davidson, I. C. M. Wehman-Ooyevaar,
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Crystallographic Data for 9: C29H31ClNOPPt, Mr = 671.06 g/mol,
¯
triclinic, P1, a = 9.6100(3) Å, b = 10.0341(5) Å, c = 14.6610(8) (Å),
α = 87.121(4)°, β = 71.029(3)°, γ = 77.209(4)°, V = 1303.40(11) Å3,
Z = 2, T = 300(1) K, 27455 total reflections, 5937 independent
[Rint = 0.028, R1 (obsd. data) = 0.026, wR2 (all data) = 0.060].
[6]
Supporting Information (see footnote on the first page of this arti-
cle): H- and C-NMR spectra of compound 9.
Acknowledgments
The authors thank the Czech Republic, Grant Agency (project
number P207/10/0215) and the Ministry of Education of the Czech
Republic (project number MSM0021627501) for financial support.
R. J. acknowledges support sponsored by the Ministry of Educa-
tion, Youth and Sports of the Czech Republic (grant project
number MSM0021627502).
[7]
Dostál, A. Ru˚zicˇka, I. Císarˇová, J. Holecˇek, Inorg. Chim. Acta
ˇ
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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L. Dostál et al.
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Published Online: ᭿
10
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Eur. J. Inorg. Chem. 0000, 0–0

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Date: 02-04-12 10:46:02
Pages: 11
Various Chelated Organogold(I) Compounds
Gold(I) Compounds
Organogold(I) compounds LAu(PPh3)
were prepared and characterized. Their
reactions with [PdCl2(CH3CN)2] and
[PtCl2(Et2S)2] complexes were investigated
and they showed promising potential for
utilization as transmetalating reagents.
M. Hejda, L. Dostál,* R. Jambor,
A. Ru˚zˇicˇka, R. Jirásko,
ˇ
J. Holecek ....................................... 1–11
Synthesis, Structure and Transmetalation
Activity of Various C,Y-Chelated Organo-
gold(I) Compounds
Keywords: Gold / Palladium / Platinum /
Metalation / Chelates
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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11