Synthesis and characterization of [3]ferrocenophane-derived P, P-chelate ligand gold complexes featuring an aurophilic interaction

Article abstract of DOI:10.1515/znb-2009-11-1223

The P, P-chelate ligand (rac)-4 was prepared starting from the α-dimethylamino-[3]ferroceno-phane by a series of directed ortho-lithiation, phosphination with ClPPh₂ and substituent exchange using HPⁱPr₂. Treatment with tw

Full text of DOI:10.1515/znb-2009-11-1223

Synthesis and Characterization of [3]Ferrocenophane-derived
P, P-Chelate Ligand Gold Complexes Featuring an Aurophilic Interaction
Gerrit Lu¨bbe, Christian Nilewski, Gerald Kehr, Roland Fro¨hlich, and Gerhard Erker
Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstraße 40, 48149 Mu¨nster, Germany
Reprint requests to Prof. Gerhard Erker. Fax: +49-251-8336503. E-mail: erker@uni-muenster.de
Z. Naturforsch. 2009, 64b, 1413 – 1422; received October 14, 2009
Dedicated to Professor Hubert Schmidbaur on the occasion of his 75th birthday
The P,P-chelate ligand (rac)-4 was prepared starting from the α-dimethylamino-[3]ferroceno-
phane by a series of directed ortho-lithiation, phosphination with ClPPh2 and substituent exchange
using HPiPr2. Treatment with two molar equivalents of (Me2S)AuCl subsequently gave the corre-
sponding κP,κP(AuCl)2 complex (rac)-9. In similar sequences the α-PCy2/o-PPh2 ligands (S,S,Spl)-
2 and the “substituent-invertomer” (R,R,Rpl)-3 (α-PPh2/o-PCy2) were prepared. Treatment with
(Me2S)AuCl in a 1 : 2 ratio gave the chelate ligand-(AuCl)2 complexes (S,S,Spl)-8 and (R,R,Rpl)-
11, respectively. The ligand (rac)-4 and the gold complexes 8, 9 and 11 were characterized by X-ray
diffraction. All three show an intramolecular Au ··· Au interaction.
Key words: Ferrocene, P,P-Chelate Ligands, Gold, Aurophilic Interaction
Introduction
markedly different catalyst performance profile [6]
(Fig. 1). In order to further characterize the functional
differences of such chelate ligands with inverted di-
arylphosphino and dialkylphosphino groups, we pre-
pared their bis(gold(I))-complexes and characterized
them spectroscopically and by X-ray diffraction. This
revealed some small but probably characteristic differ-
ences between these otherwise closely related systems.
We had recently described an efficient synthetic en-
try to P,P-chelate ligand systems based on the [3]ferro-
cenophane framework [1, 2]. The bis(diphenylphosph-
ino)[3]ferrocenophane 1 turned out to be an ideal ba-
sis for the generation of a very active Pd-based cata-
lyst system for alternating carbon monoxide/ethylene
copolymerization [3]. We have described an efficient
synthetic route to the respective highly enantiomeri-
cally enriched P,P-ligands based on a resolution pro-
cess that made each enantiomeric series easily avail-
able in high yield [4]. The unsymmetrical P,P-chelate
ligand 2 in enantiomeric form [i. e. (R,R,Rpl)-2] pro-
vided the basis for a very efficient Pd-based catalyst
for asymmetric alternating CO/propene copolymeriza-
tion [5]. Subsequently we observed that the “inverse”
P,P-ligand system 3 gave a Pd catalyst that featured a
Results and Discussion
We prepared the [3]ferrocenophane-derived P,P-
chelate ligand systems 2 and 3 each as racemates
and in both pure enantiomeric forms. In this ac-
count we will, however, only describe those sys-
tems that were actually used for the preparation of
the respective κP,κP-bis(gold(I)chloride) complexes,
namely the compounds (S,S,Spl)-2 and (R,R,Rpl)-3. In
addition we will also describe the preparation of the
-P(isopropyl)2 analog of 2, namely (rac)-4, and its uti-
lization in this chemistry.
Compound (S,S,Spl)-2 had previously been de-
scribed by us [5]. For clarity, its synthesis is briefly
outlined in Scheme 1. The preparation starts with
the enantiomerically pure [3]ferrocenophane amine
(S,S)-5. Treatment with tBuLi in hexane/ether effected
a directed metallation at the adjacent “ortho” position
at the “lower” ferrocenophane Cp ring [7] to gener-
Fig. 1. P,P-(1), P,P-(2) and its “substituent-invertomer” P,P-
chelate ligand system (3).
c
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
H3C
H3C
H3C
tBuLi
Et2O
ClPPh2
Fe
Fe
Li
Fe
Et2O
PPh2
Me2N
e2N
Me2N
[(S,S,Rpl)-6]
5
7
(S,S,Spl)-
(S,S)-
7
2
3
H3C
H3C
1
4
6
5
2 (Me2S)AuCl
CH2Cl2
HOAc
Fe
Fe
11
8
12
10
13
HPCy2
100 °C
9
14
PPh2
PCy2 PPh2
Au
Cy2P
Au
Cl
Cl
(S,S,Spl)-8
(S,S,Spl)-2
Scheme 1.
ate (S,S,Rpl)-6, which was subsequently quenched with treatment of (rac)-7 with diisopropylphosphine in
◦
diphenylchlorophosphineto yield (S,S,Spl)-7. It should freshly distilled glacial acetic acid at 115 C gave the
be noted that the pair of chiral centers in the [3]fer- P,P-chelate ligand (rac)-4 in > 90 % yield. The subse-
rocenophane system is dependent on each other, and quent reaction of (rac)-4 with two molar equivalents of
that this directed metallation process proceeds (nec- (Me2S)AuCl was carried out in dichloromethane solu-
essarily) with practically complete diastereoselectiv- tion at r. t. to yield complex (rac)-9 as a yellow solid
ity, which makes stereocontrol at the [3]ferroceno- (> 70 % isolated) (Scheme 2). Single crystals of (rac)-
phane framework with “our” specific substitution pat- 9 were obtained by diffusion of ether vapor at r. t. into
tern easy and straightforward.
a solution of the compound in CH2Cl2.
Exchange of the -NMe2 substituent in the α-
The P,P-chelate ligand 3 featuring an “inverted” at-
position of the [3]ferrocenophane bridge is carried out tachment of the -PCy2 and -PPh2 substituents relative
stereo-controlled with overall retention of the config- to 2 (see above) was prepared by simply inverting the
uration [8 – 10]. The respective two-step process is steps of the respective reaction scheme. In our spe-
initiated by protonation of the amine in acetic acid cific case directed ortho-lithiation of (R,R)-5 followed
◦
(100 C) followed by attack of the dicyclohexylphos- by quenching with ClPCy2 gave the intermediate P,N-
phine nucleophile. The process proceeds with an- chelate [3]ferrocenophane system (R,R,Rpl)-10, which
chimeric assistance of the iron center which very effec- was then converted to the P,P-chelate ligand (R,R,Rpl)-
tively controls the specific stereochemical pathway fol- 3 by treatment with HPPh2 in glacid acetic acid. The
lowed here. The resulting chelate phosphine (S,S,Spl)- product (R,R,Rpl)-3 was isolated in 72 % yield. Its sub-
2 was then reacted with the (Me2S)AuCl reagent in sequent treatment with (Me2S)AuCl in a 1 : 2 molar ra-
dichloromethane solution at r. t. to give the [κP,κP- tio in dichloromethane eventually gave the respective
(S,S,Spl)-2](AuCl)2 complex (S,S,Spl)-8 in 77 % yield κP,κP(AuCl)2 complex (R,R,Rpl)-11 in 68 % yield as
as a yellow solid. Single crystals for an X-ray crystal a yellow amorphous solid (Scheme 3). Single crys-
structure analysis were obtained from pentane/toluene tals were obtained by diffusion of pentane vapor into
by the diffusion method.
a toluene solution of this compound.
The related racemic α-PiPr2-substituted Au2-com-
The new P,P-chelate ligand (rac)-4 (see Scheme 2)
plex (rac)-9 was prepared analogously. In this case shows the typical NMR signals of the [3]ferroceno-
CH3
CH3
CH3
HOAc
2 (Me2S)AuCl
Fe
Fe
Fe
i
HP Pr2
115 °C
NMe2
PiPr2
PiPr2
Au
Ph2P
Ph2P
Ph2P
Au
Cl
Cl
(rac)-9
(rac)-4
7
(rac)-
Scheme 2.
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
1415
CH3
CH3
CH3
2 (Me2S)AuCl
CH3
1) tBuLi
HOAc
Fe
Fe
Fe
Fe
CH2Cl2
r.t.
2) ClPCy2
HPPh2
115 °C
Cy2P
Cy2P
Cy2P
NMe2
NMe2
PPh2
PPh2
Au
Au
Cl
Cl
3
5
(R,R,Rpl)-10
(R,R,Rpl)-
11
(R,R,Rpl)-
(R,R)-
Scheme 3.
Table 1. Selected 31P NMR features of the P,P-
[3]ferrocenophane ligand systems and their κP,κP(AuCl)2
complexesa.
ments of the -PPh2/-PCy2 substituents at the [3]fer-
rocenophane framework. On going from ligand 2 (o-
PPh2/α-PCy2) to ligand 3 (o-PCy2/α-PPh2) we note
a shift of the -PCy2 resonances to smaller δ values by
ca. −16 ppm and a shift of the -PPh2 signal to larger
δ values by ca. −8 ppm (see Table 1). This is as it is ex-
pected for a “transition” from a trialkylphosphine to an
aryldialkylphosphine or a triarylphosphine to an alkyl-
diarylphosphine, respectively [11]. We must, however,
note that the value of the JPP coupling constant is also
affected by this exchange – here we observe a marked
decrease of the JPP value of about 30 Hz upon go-
ing from 2 to 3. This probably indicates some differ-
ences in the stereoelectronic features between the indi-
vidual systems of the “substituent-inverted”P,P-ligand
pair 2/3.
No. o-31
P P
∆δ (o)b α-31 ∆δ (α)c JPP [Hz]
Free ligand:
o-PPh2, α-PiPr2
o-PPh2, α-PCy2
o-PCy2, α-PPh2
4
2
3
−24.6 49.3
−24.2 48.9
−16.0 51.3
11.7 41.8
9.1 39.4
−7.4 46.9
75.5
79.0
48.4
Au-complex:
o-PPh2, α-PiPr2
o-PPh2, α-PCy2
9
8
24.7
24.7
35.3
53.5
48.5
39.5
10.3
11.2
7.0
o-PCy2, α-PPh2 11
a 31P NMR spectra were recorded with a Varian INOVA 500 NMR
spectrometer (31P: 202 MHz) or a Varian Unityplus 600 NMR spec-
trometer (31P: 243 MHz) at 298 K in [D2]dichloromethane solution;
b ∆δ(o) = δ[o-31P(Au complex)]−δ[o-31P(free ligand)]; c ∆δ(α) =
δ[α-31P(Au complex)]−δ[α-31P(free ligand)].
1
phane framework (e. g. the H NMR 6-CH3 at δ =
In the gold complexes the 31P NMR resonances
1.19 (d), the corresponding 6-H signal at δ = 2.72 in the o-PCy2/α-PPh2 system 11 are close together
and the 8-HA/HB resonances at δ = 2.12/3.12). In the (∆δ ≈ 4 ppm), whereas in the “substituent-inverted” o-
κP,κP(AuCl)2-complex (rac)-4 these resonances do PPh2/α-PCy2 complex 8 they are markedly separated
not change much, as expected. However, we observe (∆δ ≈ 24 ppm). In both complexes the value of the
very typical changes of the 31P NMR resonances upon JPP coupling constants were found markedly reduced
complexation of these P,P-chelate ligands to gold (see relative to the observed values of the respective free
Table 1). The free P,P-[3]ferrocenophane system ex- ligands (see Table 1).
hibits an AX pattern of 31P NMR signals at δ = −24.6
Both the P,P-chelate ligand (rac)-4 and the corre-
(o-PPh2) and δ = +11.7 (α-PiPr2) with a very large
coupling constant of JPP = 75 Hz. Both the absolute
chemical shifts and the magnitude of the JPP coupling
constant change drastically upon complexation of the
pair of phosphorus donors to the gold atoms. The o-
PPh2 resonance is shifted to larger δ values by close
to 50 ppm and the α-PiPr2 chemical shift by > 40 ppm
(see Table 1). In the same time the value of the JPP cou-
pling constant is drastically reduced (i. e. by ca. 65 Hz)
upon complexation of the (rac)-4 P,P-chelate ligand to
the pair of gold atoms ((rac)-9).
sponding gold complex (rac)-9 were characterized by
X-ray diffraction (Fig. 2). The ligand system 4 shows
the typical structural features of the [3]ferroceno-
phane framework. The bridge shows a folded “chair-
like” geometry. This places the trans-1,3-substituents
in pseudo-axial and pseudo-equatorial positions. The
smaller of the two, the methyl group at C6, is oriented
pseudo-axially and, consequently, the bulky -PiPr2
substituent at C9 (the “α-position”) is found in an
equatorial position at the bridge. The phosphorus cen-
ter P1 shows a sum of C–P–C bond angles of 308.2◦.
Its conformation is characterized by the dihedral an-
gle C10–C9–P1–C31 of 54.6(2)◦ (C10–C9–P1–C21 =
160.4(2)◦).
Similar 31P NMR features are observed for the re-
lated free P,P-ligand (S,S,Spl)-2, and similar changes
occur in the 31P NMR spectra upon complexation to
the Au atoms (see Table 1). We observe characteris-
The -PPh2 substituent is attached at the adjacent “or-
tic changes of the 31P NMR features upon the for- tho-position” at the ferrocene moiety. It features a sum
mal mutual exchange of the positions of the attach- of C–P–C bond angles of 302.3◦ and an orientation
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
Table 2. Selected structural data of lig-
Lig. 4
9
8
11
(o-PPh2/α-PiPr2) (o-PPh2/α-PCy2) (o-PCy2/α-PPh2)
and 4 and Au2-complexes 8, 9 and 11
˚
(distances in A, angles in deg).
C9–P1
P1–Au1
Au1–Cl1
C14–P2
P2–Au2
Au2–Cl2
Au1–Au2
P1 ··· P2
1.877(2)
1.87(2)
2.247(5)
2.307(6)
1.81(2)
2.234(5)
2.305(6)
3.278(1)
4.067(8)
172.5(2)
99.2(1)
1.851(6)
2.247(2)
2.311(2)
1.804(7)
2.238(2)
2.290(2)
3.274(1)
4.123(2)
171.7(1)
101.3(1)
169.5(1)
83.5(1)
1.867(7)
2.241(2)
2.299(2)
1.811(7)
2.248(2)
2.304(2)
3.076(1)
4.185(3)
174.5(1)
99.5(1)
–
–
1.827(2)
–
–
–
3.601(1)
P1–Au1–Cl1
P1–Au1–Au2
P2–Au2–Cl2
P2–Au2–Au1
C9–P1–Au1
C14–P2–Au2
P1–C9 ··· C14–P2
P1–Au1 ··· Au2–P2
–
–
–
–
171.5(2)
89.0(1)
173.2(1)
88.9(1)
–
115.9(6)
117.2(7)
−52.7(12)
−50.3(2)
115.5(2)
117.2(2)
−55.7(4)
−60.9(1)
117.0(2)
114.4(3)
56.6(5)
–
54.3(1)
–
66.3(1)
Fig. 3. Views of the complexes (S,S,Spl)-8 (top) and
(R,R,Rpl)-11 (bottom) in the crystal.
characterized by the dihedral angles C10–C14–P2–
C41 of 159.7(2)◦ and C10–C14–P2–C51 of −98.2(2)◦.
Compound (rac)-4 takes up two equivalents of
gold(I)chloride from the (Me2S)AuCl reagent to form
the chelate κP,κP(AuCl)2 complex (rac)-9. In the
Fig. 2. Views of the free P,P-ligand (rac)-4 (top) and its cor-
responding κP,κP(AuCl)2 complex (rac)-9 (bottom) in the
crystal.
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
1417
˚
˚
crystal this features a pair of close to linear -P(R)2- amounts to 3.076(1) A, which is 0.2 A shorter as ob-
Au-Cl units that are oriented toward the same sec- served for the “substituent-invertomer” (S,S,Spl)-8. In
tor at the [3]ferrocenophane framework. They are complex 11 the angle between the P1–Au1 and P2–
found in a conformational situation that allows for Au2 vectors is 66.3(1)◦.
the formation of a weak aurophilic Au ··· Au in-
teraction [12 – 15]. We find an Au ··· Au distance
Conclusion
˚
of 3.278(1) A in (rac)-9. The resulting arrangement is
We have prepared the [3]ferrocenophane-basedP,P-
chelate ligands 2, 3 and 4, the former pair of
“substituent-invertomers” in optically active form. All
of them form κP,κP(AuCl)2 complexes when treated
with (Me2S)AuCl in a 1 : 2 molar ratio. The X-ray crys-
tal structure analyses have shown that these chelates
are geometrically suited for building up intramolecular
aurophilic interactions between the respective pairs of
gold atoms, quite different as it was recently observed
by us for a remotely related zirconocene-based P,P-
chelate ligand [16].
A comparison of the X-ray crystal structure analyses
of the “substituent-invertomeric” complexes 8 and 11
has revealed geometrically similar frameworks. Nev-
ertheless, the o-PCy2/α-PPh2 system 11 exhibits a
markedly shorter – and hence probably stronger – in-
tramolecular Au ··· Au contact, indicating that such
effects may result from an accumulation of a num-
ber of small differences in framework geometries,
which also seem to be responsible for the consider-
ably better performance of the o-PPh2/α-PCy2 P,P-
chelate ligand system 2 in Pd-catalyzed asymmet-
ric CO/propene copolymerization as compared to its
“substituent-invertomer” 3 [5, 6].
non-planar. It features dihedral angles Cl1–Au1–Au2–
Cl2 of −56.7(2)◦ and P1–Au1–Au2–P2 of −50.3(2)◦.
To allow for this interaction it was necessary to ad-
just the -PR2 conformations. We find corresponding
dihedral angles C10–C9–P1–C31 of −26.8(16)◦ and
C10–C9–P1–C21 of −139.1(14)◦ to characterize the
geometric situation at P1 in the complex. The corre-
sponding dihedral angles at the other phosphorus cen-
ter in (rac)-9 C10–C14–P2–C41 and C10–C14–P2–
C51 amount to −165.5(19)◦ and 85.0(20)◦, respec-
tively. Overall, we note that relatively small geomet-
rical changes are necessary within the ligand system to
go from (rac)-4 to (rac)-9.
The pair of “substituent-invertomeric” complexes 8
and 11 was also characterized by X-ray diffraction
(Fig. 3). Complex (S,S,Spl)-8 shows a very similar
structure as (rac)-9. It features a rotational arrange-
ment of the -PCy2 substituent at C9 (C10–C9–P1–
C31 = −37.1(5)◦, C10–C9–P1–C21 = −156.6(5)◦)
and the -PPh2 group at C14 (C10–C14–P2–C41 =
89.7(6)◦, C10–C14–P2–C51 = −160.6(6)◦) that eas-
ily allows for an aurophilic Au ··· Au interaction to
˚
be built up. With an Au ··· Au distance of 3.274(1) A
that is almost identical in strength to that found in
(rac)-9. The geometric situation around the gold-gold
vector in (S,S,Spl)-8 is characterized by dihedral an-
gles C10–C9–P1–Au1 of 85.6(4)◦, P1–Au1–Au2–P2
of −60.9(1)◦, Cl1–Au1–Au2–Cl2 of −61.6(1)◦, and
C10–C14–P2–Au2 of 40.8(6)◦ (for additional data see
Table 2.)
Experimental Section
All reactions with air- and moisture-sensitive compounds
were carried out under dry argon (Argon 5.0; Westfalen AG)
in Schlenk-type glassware. Diethyl ether, dichloromethane,
pentane, and toluene were dried using a Grubbs-type sys-
tem [17], with activated alumina (basic) or molecular sieves
as drying agents. [D2]Dichloromethane was dried over calci-
umhydride and distilled under vacuum. Commercially avail-
able reagents were used as received. NMR spectra were
recorded with a Varian 500 MHz INOVA (1H: 500 MHz,
13C: 126 MHz, 31P: 202 MHz) and a Varian UNITYplus 600
(1H: 600 MHz, 13C: 151 MHz, 31P: 243 MHz) spectrom-
eter. IR spectra were recorded for solids in pure form on
an ATR unit using a Varian 3100 FT-IR (Excalibur Series)
spectrometer. For the determination of melting points a DSC
Q 20 and a DSC 2910 CE (both of TA Instruments) were
employed. Mass spectra were collected using a MAT 312
spectrometer from Finnigan (EI) or a MicroTof instrument
Complex (R,R,Rpl)-11 shows a similar overall struc-
ture, but the formal exchange of the positions of the
attachment of the -PPh2 and -PCy2 substituents has re-
sulted in some noteworthy differences in detail. The
system features a number of changes in a variety of
parameters that make the Au ··· Au contact markedly
more favorable as compared to its congener 8 (or 9).
We observe a complex geometry of (R,R,Rpl)-11 in
the solid state that is characterized e. g. by the dihe-
dral angles around the phosphorus atoms C10–C9–P1–
C31 of 46.0(6)◦, C10–C9–P1–C21 of 153.6(5)◦, C10–
C14–P2–C41 of 155.7(7)◦, and C10–C14–P2–C51
of −87.7(8)◦. The Au ··· Au distance in (R,R,Rpl)-11 from Bruker (ESI). Elemental analyses were performed using
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1418
G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
a CHNO-Rapid analyzer (Foss-Heraeus). The compounds (dd, JP,C = 22.8 Hz, 9.7 Hz, C-8), 26.4 (d, JP,C = 10.2 Hz,
(rac)-7, (S,S,Spl)-7, (R,R,Rpl)-10 and (S,S,Spl)-2 were pre- C-6), 25.2 (dd, JP,C = 20.2 Hz, 3.3 Hz, C-9), 24.1 (d, JP,C
=
pared as previously described by us [2, 5, 18].
18.6 Hz, CHPiPrꢀ2), 23.5 (d, JP,C = 24.3 Hz, MePiPr2), 22.2
(dd, JP,C = 22.2 Hz, 3.5 Hz, CHPiPr2), 20.9 (d, JP,C = 23.7 Hz,
X-Ray crystal structure analyses: Data sets were collected
with a Nonius KappaCCD diffractometer, equipped with
a rotating anode generator. Programs used: data collection
COLLECT [19], data reduction DENZO-SMN [20], absorp-
tion correction SORTAV [21] and DENZO [22], structure solu-
tion SHELXS-97 [23], structure refinement SHELXL-97 [24],
graphics SCHAKAL [25].
CCDC 750384–750387 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data request/cif.
MePiPrꢀ2), 20.3 (d, JP,C = 3.8 Hz, MePiPr2), 17.6 (d, JP,C
=
1
2.9 Hz, MePiPrꢀ2), 16.1 (C-7). – 31P{ H} NMR (202 MHz,
298 K, [D2]dichloromethane): δ = 11.7 (d, JP,P = 75.5 Hz,
PiPr), −24.6 (d, JP,P = 75.5 Hz, PPh). – MS (ES, 70 eV): m/z
(%) = 541.2 (100) [M + H]+. – M. p. 166 ◦C. – IR (film): ν =
2960 (m), 2862 (m), 1466 (m), 1433 (s), 1261 (m), 1095 (m),
1039 (s), 1024 (m), 806 (s), 741 (s), 697 (s). – C32H38FeP2
(540.2): calcd. C 71.12, H 7.09; found C 71.07, H 7.11.
X-Ray crystal structure analysis of (rac)-4: Formula
C32H38FeP2, Mr = 540.41, yellow crystal 0.40 × 0.30 ×
0.20 mm3, monoclinic, space group P21/c (no. 14), a =
Preparation of compound (rac)-4
˚
11.2050(2), b = 14.4166(2), c = 17.7884(3) A, β
=
,
Diisopropylphosphine (0.974 g, (10 % solution in hex-
ane), 0.825 mmol, 1.1 eq.) was added to a solution of
(rac)-7 (350 mg, 0.75 mmol, 1.0 eq.) in freshly distilled
glacial acetic acid (15 mL). The mixture was kept at 115 ◦C
for 48 h and afterwards cooled down to r. t. After addition of
dichloromethane (20 mL), saturated aqueous sodium bicar-
bonate (400 mL) was cautiously added in small portions un-
til the gas evolution had ceased. The aqueous phase was ex-
tracted with dichloromethane. The combined organic phases
were dried over magnesium sulfate, filtered and concentrated
in vacuo. The residue was dissolved in dichloromethane
(3 mL) and precipitated with n-pentane (10 mL). Purifica-
tion of the crude material was obtained by column chro-
◦
3
91.332(1) , V = 2872.73(8) A , Z = 4, ρcalc = 1.25 g cm−3
˚
µ = 0.7 mm−1, empirical absorption correction (0.780 ≤ T ≤
˚
0.880), λ = 0.71073 A, T = 223 K, ω and ϕ scans, 18115−re1-
˚
flections collected ( h, k, l), [(sinθ)/λ] = 0.67 A
,
7047 independent (Rint = 0.037) and 4736 observed re-
flections [I ≥ 2σ(I)], 321 refined parameters, R = 0.049,
wR2 = 0.126, max. (min.) residual electron density 0.65
(−0.60) e A−3. Comments: Hydrogen atoms calculated and
˚
refined as riding atoms.
Synthesis of complex (rac)-9
A reaction flask was charged with 54.5 mg (Me2S)AuCl
matography on silica gel (cyclohexane, ethyl acetate, 1 : 1; (0.19 mmol, 2.0 eq.) and CH2Cl2 (15 mL). After the drop-
Rf = 0.8) to give pure (rac)-4 (380 mg, 0.70 mmol, 93 %). wise addition of a CH2Cl2 (10 mL) solution of 50 mg
Single crystals suitable for X-ray diffraction, were obtained (0.095 mmol, 1.0 eq.) of (rac)-4, the solution was stirred
by slow diffusion of a saturated dichloromethane solution. – for 1 h at r. t. Then the solvent was reduced to 3 mL in vacuo.
1H NMR (600 MHz, 298 K, [D2]dichloromethane): δ = 7.47 After the addition of 15 mL of diethyl ether the product pre-
(m, 2H, o-PPh2), 7.31 (m, 5H, o, m, p-PPh2), 7.25 (m, 3H, cipitated as a yellow powder (75 mg, 0.07 mmol, 74 %).
m, p-PPh2), 4.29 (m, 1H, H-5), 4.19 (m, 1H, H-12), 4.18 Yellow single crystals were obtained by slow diffusion of
(m, 1H, H-11), 4.08 (m, 1H, H-2), 3.84 (m, 1H, H-3), 3.82 diethyl ether into a dichloromethane solution of (rac)-9 at
(m, 1H, H-13), 3.39 (m, 1H, H-4), 3.12 (m, 1H, H-8B), 2.72 r. t. – 1H NMR (500 MHz, 298 K, [D2]dichloromethane):
3
(m, 1H, H-6), 2.46 (ddd, JH,H = 12.8 Hz, 4.7 Hz, 1.9 Hz, δ = 7.73 (m, 2H, o-PPh2), 7.55 (m, 2H, o-PPhꢀ2), 7.55 (m,
3
1H, H-9), 2.12 (m, 1H, H-8A), 1.73 (sept, JH,H = 6.4 Hz, 1H, p-PPh2), 7.51 (m, 1H, p-PPhꢀ2), 7.51 (m, 2H, m-PPh2),
1H, CHPiPr), 1.20 (sept, 3JH,H = 6.4 Hz, 1H, CHPiPrꢀ), 1.19 7.45 (m, 2H, m-PPhꢀ2), 5.03 (m, 1H, H-5), 4.44 (m, 1H,
3
3
(d, JH,H = 7.7 Hz, 1H, H-7), 1.18 (dd, JH,H = 7.9 Hz, H-13), 4.42 (m, 1H, H-11), 4.34 (m, 1H, H-8B), 4.25 (m,
7.3 Hz, 1H, MePiPr2), 1.17 (dd, 3JH,H = 14.7 Hz, 7.4 Hz, 1H, 1H, H-2), 4.03 (m, 1H, H-3), 3.82 (m, 1H, H-4), 3.78 (m,
MePiPr2), 0.90 (dd, JH,H = 7.2 Hz, 5.4 Hz, 1H, MePiPrꢀ2), 1H, H-12), 2.99 (m, 1H, H-6), 2.88 (m, 1H, H-9), 2.37 (m,
3
0.40 (dd, 3JH,H = 15.6 Hz, 7.4 Hz, 1H, MePiPrꢀ2). – 13C{ H} 1H, H-8A), 2.36 (m, 1H, CHPiPr), 1.57 (m, 1H, CHPiPrꢀ),
1
NMR (151 MHz, 298 K, [D2]dichloromethane): δ = 140.6 1.34 (d, JH,H = 7.2 Hz, 3H, MePiPr2), 1.31 (d, JH,H
=
1
1
(d, JP,C = 8.9 Hz, i-PPh2), 139.2 (dd, JP,C = 13.9 Hz, 7.3 Hz, 3H, MePiPr2), 1.24 (d, JH,H = 7.3 Hz, 3H, H-7),
5.7 Hz, i-PPh2), 135.3 (d, JP,C = 21.4 Hz, o-PPh2), 133.4 1.05 (dd, JH,H = 13.0 Hz, 7.3 Hz, 3H, MePiPrꢀ2), 0.63 (dd,
1
(d, JP,C = 19.4 Hz, o-PPh2), 128.8 (p-PPh2), 128.2 (d, JP,C
=
JH,H = 18.0 Hz, 7.0 Hz, 3H, MePiPrꢀ2). – 13C{ H} NMR
7.3 Hz, m-PPh2), 128.03 (d, JP,C = 7.0 Hz, m-PPh2), 127.97 (125.6 MHz, 298 K, [D2]dichloromethane): δ = 135.6 (d,
(p-PPh2), 93.1 (dd, JP,C = 22.3, 12.5 Hz, C-10), 92.0 (C-1), JP,C = 13.0 Hz, o-PPh2), 134.9 (d, JP,C = 14.3 Hz, o-PPhꢀ2),
75.6 (dd, JP,C = 5.3, 2.1 Hz, C-11), 74.8 (d, JP,C = 4.6, 132.3 (d, JP,C = 2.6 Hz, p-PPh2), 131.8 (d, JP,C = 2.3 Hz,
C-13), 73.2 (d, JP,C = 15.8 Hz, C-14), 72.3 (d, JP,C = 4.8 Hz,
p-PPhꢀ2), 131.2 (d, JP,C = 61.7 Hz, i-PPhꢀ2), 129.6 (d, JP,C
=
C-5), 70.1 (C-4), 69.6 (C-12), 69.1 (C-2), 67.9 (C-3), 45.8 63.0 Hz, i-PPh2), 129.4 (d, JP,C = 12.0 Hz, m-PPh2), 128.9
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
1419
(d, JP,C = 11.5 Hz, m-PPhꢀ2), 92.8 (C-1), 86.2 (dd, JP,C
=
(d, JP,C = 13.2 Hz, o-PPh2), 135.0 (d, JP,C = 14.3 Hz,
13.3 Hz, 2.9 Hz, C-10), 79.4 (dd, JP,C = 8.4 Hz, 3.7 Hz, o-PPhꢀ2), 132.1 (d, JP,C = 2.6 Hz, p-PPh2), 131.8 (d, JP,C
=
C-11), 79.0 (d, JP,C = 5.7 Hz, C-12), 73.8 (d, JP,C = 2.0 Hz, 2.5 Hz, p-PPhꢀ2), 131.6 (d, JP,C = 61.3 Hz, i-PPhꢀ2), 130.3
C-5), 72.5 (C-4), 71.9 (d, JP,C = 7.1 Hz, C-13), 70.4 (C-2), (d, JP,C = 63.5 Hz, i-PPh2), 129.4 (d, JP,C = 11.5, m-PPh2),
70.1 (C-3), 68.6 (d, JP,C = 62.8 Hz, C-14), 47.0 (dd, JP,C
=
128.8 (d, JP,C = 11.8 Hz, m-PPhꢀ2), 92.8 (C-1), 86.1 (dd,
8.6 Hz, 2.0 Hz, C-8), 28.5 (dd, JP,C = 28.0 Hz, 1.6 Hz, C-9), JP,C = 13.2 Hz, 3.2 Hz, C-10), 79.3 (dd, JP,C = 8.8 Hz,
27.4 (d, JP,C = 31.7 Hz, CHPiPrꢀ), 27.0 (d, JP,C = 27.5 Hz, 3.8 Hz, C-11), 79.0 (d, JP,C = 5.5 Hz, C-13), 73.7 (d, JP,C
=
CHPiPr), 26.1 (d, JP,C = 11.5 Hz, C-6), 22.2 (d, JP,C = 6.2 Hz, 1.8 Hz, C-5), 72.5 (C-4), 72.1 (d, JP,C = 7.2 Hz, C-12),
MePiPrꢀ2), 21.8 (d, JP,C = 1.2 Hz, MePiPr2), 21.0 (MePiPr2), 70.4 (C-2), 70.0 (C-3), 68.2 (d, JP,C = 62.7 Hz, C-14), 46.5
1
17.6 (d, JP,C = 4.9 Hz, MePiPrꢀ2), 16.2 (C-7). – 31P{ H} (dd, JP,C = 8.2 Hz, 2.0 Hz, C-8), 37.8 (d, JP,C = 30.8 Hz,
NMR (202 MHz, 298 K, [D2]dichloromethane): δ = 53.5 CHPCyꢀ), 37.2 (d, JP,C = 26.2 Hz, CHPCy), 33.2 (CH2PCy2),
(d, JP,P = 10.3 Hz, PiPr), 24.7 (d, JP,P = 10.3 Hz, PPh). – 32.3 (d, JP,C = 4.8 Hz, CH2PCy2), 31.2 (CH2PCy2), 29.1 (d,
HRMS ((+)-ESI): m/z = 1027.0387 (calcd. 1027.0400 for JP,C = 5.3 Hz, CH2PCy2), 27.9 (d, JP,C = 12.7 Hz, CH2PCy2),
C32H38Au2FeP2Cl2Na, [M+Na]+). – M. p. 259 ◦C. – IR 27.7 (d, JP,C = 11.2 Hz, CH2PCy2), 27.5 (d, JP,C = 9.3 Hz,
(film): ν = 2957 (m), 2870 (m), 1458 (s), 1458 (m), 1436 CH2PCy2), 27.4 (d, JP,C = 14.9 Hz, CH2PCy2), 26.5 (dd,
(s), 1384.5 (m), 1146 (s), 1096 (s), 1054 (w), 1030 (w), 815 JP,C = 28.2 Hz, 1.8 Hz, C-9), 26.4 (d, JP,C = 1.5 Hz,
(w), 753 (s), 696 (s). – C32H38Au2Cl2FeP2 (1004.1): calcd. CH2PCy2), 26.2 (d, JP,C = 1.3 Hz, CH2PCy2), 26.1 (d, JP,C
=
1
C 38.23, H 3.81; found C 37.87, H 3.77.
11.5 Hz, C-6), 16.4 (C-7). – 31P{ H} NMR (202 MHz,
X-Ray crystal structure analysis of (rac)-9: Formula 298 K, [D2]dichloromethane): δ = 48.5 (d, JP,P = 11.2 Hz,
1
C32H38Au2Cl2FeP2 · /2 CH2Cl2, Mr = 1047.71, yellow crys- PCy), 24.7 (d, JP,P = 11.2 Hz, PPh). – HRMS ((+)-ESI):
tal 0.30×0.03×0.02 mm3, monoclinic, space group P21/n m/z = 1049.1423 (calcd. 1049.1439 for C38H46Au2FeP2Cl,
(no. 14), a = ◦9.0973(3), b = 16.0397(4), c = 23.7200(8) A, [M]+). – M. p. decomposition at 267 C. – IR (film): ν =
◦
˚
3
β = 90.456(2) , V = 3461.1(2) A , Z = 4, ρcalc = 2.01 g cm−3
,
2923 (s), 2852 (s), 2360 (w), 1436 (s), 1176 (m), 1150
˚
µ = 9.2 mm−1, empirical absorption correction (0.169 ≤ (m), 1095 (s), 999 (s), 812 (m), 747 (s), 695 (s), 642 (s). –
˚
T ≤ 0.837), λ = 0.71073 A, T = 223 K, ω and ϕ scans, C38H46Au2Cl2FeP2 (1084.1): calcd. C 42.05, H 4.27;
27171 reflections collected ( h, k, l), [(sinθ)/λ] = found C 42.49, H 4.16. – [α]2D0 (589 nm) = −74 (c =
0.54 A−1, 4451 independent (Rint = 0.124) and 3465 ob- 1·10−3 g mL−1, CH2Cl2).
˚
served reflections [I ≥ 2σ(I)], 369 refined parameters, R =
X-Ray crystal structure analysis of 8: formula
0.078, wR2 = 0.190, max. (min.) residual electron density C38H46Au2Cl2FeP2 · 2 C7H8, Mr
= 1269.64, yellow
1.96 (−2.90) e A−3. Comments: Hydrogen atoms calcu- crystal 0.60 × 0.10 × 0.10 mm3, orthorhombic, space
˚
lated and refined as riding atoms; due to the shape and the group P212121 (no. 19), a = 9.6050(1), b = 20.9797(3),
3
˚
˚
size of the investigated crystal the quality of the analysis is c = 24.4364(4) A, V = 4924.18(12) A , Z = 4, ρcalc
=
limited.
1.71 g cm−3 6.4 mm−1
, µ = , empirical absorption
˚
correction (0.113 ≤ T ≤ 0.565), λ = 0.71073 A, T =
Synthesis of complex (S,S,S )-8
223 K, ω and ϕ scans, 27573 reflections collected ( h,
pl
k, l), [(sinθ)/λ] = 0.66 A−1, 11333 independent
˚
47 mg (Me2S)AuCl (0.16 mmol, 2.0 eq.) was dissolved
in CH2Cl2 (15 mL). After the addition of 50 mg (0.08 mmol,
1.0 eq.) of (S,S,Spl)-2, the solution was stirred for 1 h
at r. t. Then the solvent was reduced to 5 mL in vacuo.
After the addition of 8 mL of diethyl ether the product
was precipitated as a yellow powder (67 mg, 0.062 mmol,
77 %). – 1H NMR (500 MHz, 298 K, [D2]dichloromethane):
δ = 7.69 (m, 2H, o-PPh2), 7.55 (m, 2H, o-PPhꢀ2), 7.53 (m,
1H, p-PPh2), 7.52 (m, 2H, m-PPh2), 7.50 (m, 1H, p-PPhꢀ2),
7.44 (m, 2H, m-PPhꢀ2), 5.01 (m, 1H, H-5), 4.45 (m, 1H,
H-12), 4.39 (m, 1H, H-11), 4.37 (m, 1H, H-8B), 4.24 (m,
(Rint = 0.054) and 9652 observed reflections [I ≥ 2σ(I)],
441 refined parameters, R = 0.036, wR2 = 0.090, Flack
parameter: −0.023(6), max. (min.) residual electron den-
sity 0.96 (−1.06) e A−3. Comments: Hydrogen atoms
˚
calculated and refined as riding atoms; solvent molecules
refined with geometrical restraints and isotropic thermal
parameters.
Preparation of compound (R,R,R )-3
pl
Diphenylphosphine (0.13 mL, 0.71 mmol, 1.1 eq.) was
1H, H-2), 4.01 (m, 1H, H-3), 3.82 (m, 1H, H-13), 3.75 (m, added with exclusion of light to a solution of (R,R,Rpl)-
1H, H-4), 3.00 (m, 2H, H-9, H-6), 2.35 (m, 1H, H-8A), 10 (310 mg, 0.65 mmol, 1.0 eq.) in freshly distilled glacial
2.09 (m, 1H, CHPCy), 1.36 (m, 1H, CHPCyꢀ), 2.17/1.56, acetic acid (15 mL). The mixture was kept at 115 ◦C
2.08/1.48, 1.87/1.32, 1.84/1.32, 1.82/1.24, 1.74/0.92, for 20 h and afterwards cooled to r. t. After addition of
1.71/1.24, 1.59/1.09, 1.58/0.97, 1.18/1.18 (each m, each 1H, dichloromethane (20 mL), saturated aqueous sodium bicar-
1
CH2PCy2), 1.23 (d, JH,H = 7.2 Hz, 3H, H-7). – 13C{ H} bonate (400 mL) was added in small portions until the gas
NMR (126 MHz, 298 K, [D2]dichloromethane): δ = 135.3 evolution ceased. The aqueous phase was extracted with
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1420
G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
dichloromethane. The combined organic phases were dried (0.08 mmol, 1.0 eq.) of (R,R,Rpl)-3 in a CH2Cl2 (10 mL)
(magnesium sulfate), filtered and concentrated in vacuo. solution, the reaction was stirred for 1 h at r. t. The sol-
The residue was suspended in ethanol (15 mL), and a few vent was reduced to 5 mL in vacuo. After the addition of
drops of dichloromethane were ◦added until complete so- 10 mL of pentane the product was precipitated as a yellow
lution. This was stored at −32 C for 12 h, and the pre- powder (59 mg, 0.05 mmol, 68 %). Yellow single crystals
cipitate was collected. Purification of the crude material were obtained by slow diffusion of pentane into a toluene so-
1
was carried out by column chromatography with silica gel lution of (R,R,Rpl)-11 at r. t. – H NMR (600 MHz, 298 K,
(cyclohexane, ethyl acetate, 1 : 1; Rf = 0.4) to give pure [D2]dichloromethane): δ = 7.96 (m, 2H, o-PPh2), 7.93 (m,
(R,R,Rpl)-3 (286 mg, 0.46 mmol, 72 %). By slow diffusion 2H, o-PPhꢀ2), 7.53 (m, 1H, p-PPh2), 7.52 (m, 2H, m-PPh2),
of n-pentane in a saturated dichloromethane solution sin- 7.45 (m, 1H, p-PPhꢀ2), 7.42 (m, 2H, m-PPhꢀ2), 4.49 (m, 1H,
gle crystals suitable for X-ray diffraction were obtained. H-5), 4.46 (m, 1H, H-12), 4.45 (m, 1H, H-11), 4.28 (m, 1H,
1H NMR (500 MHz, 298 K, [D2]dichloromethane): δ = H-8B), 4.24 (m, 1H, H-2), 4.18 (m, 1H, H-13), 4.17 (m, 1H,
7.65 (m, 2H, o-PPh), 7.46 (m, 2H, o-PPhꢀ), 7.38 (m, 3H, H-3), 4.02 (m, 1H, H-4), 3.41 (dd, J = 18.8 Hz, 12.0 Hz, 1H,
m/p-PPh), 7.21 (m, 3H, m/p-PPhꢀ), 4.16 (m, 1H, H-13), H-9), 2.81/1.68, 2.46/1.65, 2.08/1.65, 1.93/1.40, 1.90/1.37,
4.15 (m, 1H, H-11), 4.11 (m, 1H, H-2), 4.05 (m, 1H, 1.74/1.14, 1.72/1.35, 1.49/1.15, 1.43/0.23, 1.24/1.24 (each
H-12), 4.00 (m, 1H, H-3), 3.98 (m,1H, H-5), 3.92 (m, 1H, m, each 1H, CH2PCy2), 2.68 (m, 1H, H-6), 2.30 (m, 1H,
H-4), 3.07/1.75 (each m, each 1H, H-8A/B), 3.05 (m, 1H, CHPCy), 2.12 (m, 2H, H-8A), 1.75 (m, 1H, CHPCyꢀ), 0.81
1
H-9), 2.46/1.39, 1.97/1.37, 1.84/1.37, 1.83/1.35, 1.75/1.35, (d, JH,H = 7.2 Hz, 3H, H-7). – 13C{ H} NMR (151 MHz,
1.73/1.33, 1.60/1.23, 1.57/0.81, 1.56/1.09, 1.55/1.10 (each 298 K, [D2]dichloromethane): δ = 134.7 (d, JP,C = 13.1 Hz,
m, each 1H, CH2PCy2), 2.45 (m, 1H, H-6), 2.04 (m, o-PPhꢀ2), 134.5 (d, JP,C = 14.1 Hz, o-PPh2), 132.5 (d, JP,C
=
3
1H, CHPCy), 1.67 (m, 1H, CHPCyꢀ), 0.97 (d, JH,H
=
2.6 Hz, p-PPh2), 132.3 (d, JP,C = 2.7 Hz, p-PPhꢀ2), 131.9 (d,
1
7.2 Hz, 3H, H-7). – 13C{ H} NMR (126 MHz, 298 K, JP,C = 55.4 Hz, i-PPh2), 129.9 (d, JP,C = 55.4 Hz, i-PPhꢀ2),
[D2]dichloromethane): δ = 140.2 (dd, JP,C = 19.6 Hz, 1.7 Hz, 129.6 (d, JP,C = 11.4, m-PPh2), 129.3 (d, JP,C = 10.6 Hz, m-
i-PPh), 139.4 (dd, JP,C = 17.9 Hz, 1.8 Hz, i-PPhꢀ), 134.3 PPhꢀ2), 94.2 (C-1), 83.0 (m, C-10), 79.2 (m, C-11), 76.3 (d,
(d, JP,C = 22.2 Hz, o-PPh), 133.3 (d, JP,C = 18.3 Hz, o- JP,C = 4.9 Hz, C-13), 73.5 (C-4), 72.6 (C-5), 71.3 (d, JP,C
=
PPhꢀ), 129.5 (d, JP,C = 1.0 Hz, p-PPh), 128.7 (d, JP,C
=
51.9 Hz, C-14), 71.0 (d, JP,C = 6.0 Hz, C-12), 70.14 (C-2),
7.8 Hz, m-PPh), 128.5 (p-PPhꢀ), 128.2 (d, JP,C = 6.2 Hz, m- 70.09 (C-3), 46.5 (dd, JP,C = 13.2 Hz, 1.9 Hz, C-8), 42.3 (dd,
PPhꢀ), 93.4 (C-1), 89.4 (dd, JP,C = 18.5 Hz, 16.6 Hz, C-10), JP,C = 33.0 Hz, 1.0 Hz, CHPCyꢀ), 37.2 (d, JP,C = 33.6 Hz,
78.7 (d, JP,C = 25.9 Hz, C-14), 75.7 (dd, JP,C = 4.3 Hz, CHPCy), 34.6 (dd, JP,C = 32.6 Hz, 1.5 Hz, H-9), 33.8 (d,
2.2 Hz, C-11), 72.4 (dd, JP,C = 4.5 Hz, 1.0 Hz, C-12), 72.3 JP,C = 3.4 Hz, CH2PCy2), 31.8 (d, JP,C = 2.4 Hz, CH2PCy2),
(d, JP,C = 2.7 Hz, C-5), 71.1 (C-4), 68.8 (C-2), 68.7 (C-13), 31.3 (d, JP,C = 1.8 Hz, CH2PCy2), 28.0 (d, JP,C = 14.9 Hz,
67.8 (C-3), 45.2 (dd, JP,C = 23.6 Hz, 11.8 Hz, C-8), 39.3 (dd, CH2PCy2), 27.8 (d, JP,C = 3.2 Hz, CH2PCy2), 27.2 (d, JP,C
=
JP,C = 13.5 Hz, 7.8 Hz, CHPCyꢀ), 34.7 (dd, JP,C = 14.1 Hz, 14.4 Hz, CH2PCy2), 27.1 (d, JP,C = 13.4 Hz, CH2PCy2),
2.3 Hz, CHPCy), 33.3 (d, JP,C = 20.2 Hz, CH2PCy2), 32.7 26.7 (d, JP,C = 11.0 Hz, CH2PCy2), 26.1 (d, JP,C = 1.5 Hz,
(dd, JP,C = 18.9 Hz, 3.4 Hz, CH2PCy2), 31.1 (d, JP,C
=
CH2PCy2), 26.0 (d, JP,C = 1.9 Hz, CH2PCy2), 25.6 (d, JP,C
=
1
11.0 Hz, CH2PCy2), 30.7 (dd, JP,C = 14.1 Hz, 2.0 Hz, C-9), 13.0 Hz, H-6), 15.5 (C-7). – 31P{ H} NMR (202 MHz,
28.4 (d, JP,C = 5.1 Hz, CH2PCy2), 28.4 (d, JP,C = 12.7 Hz, 298 K, [D2]dichloromethane): δ = 39.5 (d, JP,P = 7.0 Hz,
CH2PCy2), 28.1 (d, JP,C = 12.5 Hz, CH2PCy2), 27.8 (d, JP,C
=
PPh), 35.3 (d, JP,P = 7.0 Hz, PCy). – HRMS ((+)-ESI): m/z =
5.4 Hz, CH2PCy2), 27.7 (d, JP,C = 8.2 Hz, CH2PCy2), 26.9 (m, 1107.1019 (calcd. 1107.1026 for C38H46Au2FeP2Cl2Na,
2C, CH2PCy2), 26.0 (d, JP,C = 11.1 Hz, C-6), 16.1 (C-7). – [M+Na]+). – M. p. decomposition at 290 C. – IR (film):
◦
1
31P{ H} NMR (202 MHz, 298 K, [D2]dichloromethane): ν = 2927 (s), 2851 (s), 1436 (s), 1177 (m), 1147 (m), 1099
4
δ = −7.4 (d, JP,P = 48.4 Hz, ν1/2 ∼ 3 Hz, PPh), −16.0 (s), 999 (w), 746 (s), 692 (s), 545 (m). – C38H46Au2FeP2Cl2
4
(1004.1): calcd. C 42.05, H 4.27; found C 42.23, H 4.12. –
(d, JP,P = 48.4 Hz, ν1/2 ∼ 15 Hz, PCy). – C38H46FeP2
[α]2D0 (589 nm) = −93 (c = 1·10−3 g mL−1, CH2Cl2).
(620.2): calcd. C 73.55, H 7.47; found C 73.20, H 7.24. –
[α]2D0 (589 nm) = 52 (c = 1 · 10−3 g mL−1, CH2Cl2). [From
X-Ray crystal structure analysis of 11: formula
(rac)-3: HRMS ((+)-ESI): m/z = 621.2493 (calcd. 621.2498
C38H46Au2Cl2FeP2 · CH2Cl2, Mr
=
1170.30, yellow
for C38H46FeP2H, [M+H]+). – M. p. 220 ◦C. – IR (film): ν =
3088 (m), 2922 (s), 2842 (m), 1441 (m), 1263 (w), 1086 (w),
1026 (w), 812 (w), 741 (w), 698 (w) cm−1].
crystal 0.30 × 0.30 × 0.03 mm3, orthorhombic, space
group P212121 (no. 19), a = 9.6258(1), b = 18.5462(3),
3
˚
˚
c = 21.9882(3) A, V = 3925.38(9) A , Z = 4, ρcalc
=
1.98 g cm−3, µ = 8.2 mm−1, empirical absorption cor-
Synthesis of complex (R,R,R )-11
pl
˚
rection (0.192 ≤ T ≤ 0.791), λ = 0.71073 A, T = 223 K,
47 mg (Me2S)AuCl (0.16 mmol, 2.0 eq.) was dissolved ω and ϕ scans, 31688 reflections collected ( h, k, l),
in CH2Cl2 (15 mL). After the dropwise addition of 50 mg [(sinθ)/λ] = 0.66 A−1, 9352 independent (Rint = 0.094)
˚
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G. Lu¨bbe et al. · [3]Ferrocenophane-derived P,P-Chelate Ligand Gold Complexes
1421
and 8120 observed reflections [I ≥ 2σ(I)], 434 refined Acknowledgements
parameters, R = 0.043, wR2 = 0.109, Flack parameter:
−0.019(7), max. (min.) residual electron density 1.34
Financial support from the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie is gratefully
acknowledged. We thank the BASF for a gift of solvents.
(−1.90) e A−3. Comments: Hydrogen atoms calculated and
˚
refined as riding atoms.
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