Diphenylphosphinoferrocene gold(I) acetylides: Synthesis of heterotri- And heterotetrametallic transition metal complexes

Article abstract of DOI:10.1021/om701021y

The synthesis and reaction chemistry of heterobimetallic FcPPh ₂AuCl (1) and FcPPh₂Au-C≡CR compounds (3a, R = bipy; 3b, R = C₆H₄-4-C≡N; 3c, R = C₅H ₄N-4; 3d, R = NCN-H; 3e, R = NCN-I; Fc = (η⁵-C ₅H₅)(η⁵-C₅H₄)Fe; bipy = 2,2′-bipyridyl-5-yl; NCN = [C₆H₂(CH ₂NMe₂)₂-2,6]^-) toward diverse organometallic molecules is described. In context with this background, 1 was prepared by reacting FcPPh₂ with (tht)AuCl (tht = tetrahydrothiophene). The reaction of 1 either with HC≡CR (2a, R = bipy; 2b, R = C₆H₄-4-C≡N; 2c, R = C₅H ₄N-4) or with the lithium acetylides LiC≡CR (2d, R = NCN-H; 2e, R = NCN-I) gave complexes 3a-3e in good yield. In 1 the gold(I) chloride entity was further reacted with the organometallic alkyne HC≡CML_n (4a, ML_n = (η-C₆H₅)Cr(CO)₃; 4b, ML_n = Fc; 4c, ML_n = Rc; Rc = (η⁵-C ₅H₅)(η⁵-C₅H₄)Ru) to afford the heterotrimetallic complexes FcPPh₂Au-C≡CML _n (5a, ML_n = (η⁶-C₆H ₅)Cr(CO)₃; 5b, ML_n = Fc; 5c, ML_n = Rc) in which three different transition metal atoms are connected via rigid-rod structured carbon-rich units. Complexes 3a-3e feature with their terminal nitrogen donor groups a further binding site, which allows the introduction of a third metal-containing fragment. In this context, the reaction of 3b with [Ru]N≡N[Ru] (6) ([Ru] = [η³-mer-(2,6-(Me ₂NCH₂)₂C₅H₃N}-RuCl ₂]) resulted in the formation of neutral heterotrimetallic FcPPh ₂Au-C≡C-C₆H₄-4-C≡N-[Ru] (7). The synthesis of an even heterotetrametallic complex [FcPPh₂Au-C≡C- C₅H₄N-Cu {(Me₃SiC≡C)₂[Ti]}]OTf (9) could be achieved by treatment of 3c with the organometallic π-tweezer {[Ti](μ-σ,π-C≡CSiMe₃)₂} CuOTf (8a). Heterobimetallic 3a afforded in a straightforward reaction with equimolar amounts of (nbd)Mo(CO)₄ (14) (nbd = 1,5-norbornadiene) and {[Ti](μ-σ,π-C≡CSiMe₃)₂}MX (8b, M = Cu(N≡CMe), X = PF₆; 8c, M = Ag, X = OClO₃), respectively, compounds FcPPh₂Au-C≡C-bipy[Mo(CO)₄] (15) and (FcPPh₂Au-C≡C-bipy[{[Ti](μ-σ,π- C≡CSiMe₃)₂}M])X (16a, M = Cu, X = PF₆; 16b, M = Ag, X = ClO₄). The synthesis of the Fe-Au-Pt NCN pincer molecule FcPPh₂Au-C≡C-NCN-Pt-C=CR (13a, R = bipy; 13b, R = C₆H₄-4-C≡N) was possible by the consecutive reaction of Me₃SiC=C-NCN-PtCl (10) with Li-2a or Li-2b to give Me ₃SiC≡C-NCN-Pt-C=CR (11a, R = bipy; lib, R = C₆H ₄-4-C≡N), which with [n-Bu₄N]F produced HC≡C-NCN-Pt-C=CR (12a, R = bipy; 12b, R = C₆H ₄-4-C≡N). On reacting 12a and 12b with 1, complexes 13a and 13b were formed, which are highly insoluble, and hence, no further reactions were carried out. The solid state structures of 3a, 3b, 3e, 5b, 5c, and 16a are reported. Most characteristic for these complexes is that the appropriate transition metals are linked by carbon-rich organic bridging units. The electrochemical properties of selected samples (3a-3c, 5a-5c, 7, 9, 16a, and 16b) are reported. The cyclovoltammetric data show that there is no significant influence of the organic and organometallic acetylide units on the redox potential of the diphenylphosphino ferrocene in 3a- 3c and 5a-5c. Remarkable is that the chelate coordination of the bipyridyl unit to Cu(I) in 16a results in a reduction of Cu(I) followed by reoxidation of Cu(0) without any structural change of the molecule involved, which is unique in titanium(IV)-copper(I) chemistry.

Full text of DOI:10.1021/om701021y

1214
Organometallics 2008, 27, 1214–1226
Diphenylphosphinoferrocene Gold(I) Acetylides: Synthesis of
Heterotri- and Heterotetrametallic Transition Metal Complexes
Rico Packheiser, Alexander Jakob, Petra Ecorchard, Bernhard Walfort, and Heinrich Lang*
Institut für Chemie, Lehrstuhl für Anorganische Chemie, Fakultät für Naturwissenschaften, Technische
UniVersität Chemnitz, Strasse der Nationen 62, 09111 Chemnitz, Germany
ReceiVed October 11, 2007
The synthesis and reaction chemistry of heterobimetallic FcPPh2AuCl (1) and FcPPh2Au-CtCR
compounds (3a, R ) bipy; 3b, R ) C6H4-4-CtN; 3c, R ) C5H4N-4; 3d, R ) NCN-H; 3e, R ) NCN-I;
Fc ) (η5-C5H5)(η5-C5H4)Fe; bipy ) 2,2′-bipyridyl-5-yl; NCN ) [C6H2(CH2NMe2)2-2,6]-) toward diverse
organometallic molecules is described. In context with this background, 1 was prepared by reacting FcPPh2
with (tht)AuCl (tht ) tetrahydrothiophene). The reaction of 1 either with HCtCR (2a, R ) bipy; 2b, R
) C6H4-4-CtN; 2c, R ) C5H4N-4) or with the lithium acetylides LiCtCR (2d, R ) NCN-H; 2e, R )
NCN-I) gave complexes 3a-3e in good yield. In 1 the gold(I) chloride entity was further reacted with
the organometallic alkyne HCtCMLn (4a, MLn ) (η6-C6H5)Cr(CO)3; 4b, MLn ) Fc; 4c, MLn ) Rc; Rc
) (η5-C5H5)(η5-C5H4)Ru) to afford the heterotrimetallic complexes FcPPh2Au-CtCMLn (5a, MLn )
(η6-C6H5)Cr(CO)3; 5b, MLn ) Fc; 5c, MLn ) Rc) in which three different transition metal atoms are
connected via rigid-rod structured carbon-rich units. Complexes 3a-3e feature with their terminal nitrogen
donor groups a further binding site, which allows the introduction of a third metal-containing fragment.
In this context, the reaction of 3b with [Ru]NtN[Ru] (6) ([Ru] ) [η3-mer-{2,6-(Me2NCH2)2C5H3N}-
RuCl2]) resulted in the formation of neutral heterotrimetallic FcPPh2Au-CtC-C6H4-4-CtN-[Ru] (7).
The synthesis of an even heterotetrametallic complex [FcPPh2Au-CtC-C5H4N-Cu{(Me3SiCtC)2[Ti]}]OTf
(9) could be achieved by treatment of 3c with the organometallic π-tweezer {[Ti](µ-σ,π-
CtCSiMe3)2}CuOTf (8a). Heterobimetallic 3a afforded in a straightforward reaction with equimolar
amounts of (nbd)Mo(CO)4 (14) (nbd ) 1,5-norbornadiene) and {[Ti](µ-σ,π-CtCSiMe3)2}MX (8b, M
) Cu(NtCMe), X ) PF6; 8c, M ) Ag, X ) OClO3), respectively, compounds FcPPh2Au-CtC-
bipy[Mo(CO)4] (15) and (FcPPh2Au-CtC-bipy[{[Ti](µ-σ,π-CtCSiMe3)2}M])X (16a, M ) Cu, X )
PF6; 16b, M ) Ag, X ) ClO4). The synthesis of the Fe-Au-Pt NCN pincer molecule FcPPh2Au-CtC-
NCN-Pt-CtCR (13a, R ) bipy; 13b, R ) C6H4-4-CtN) was possible by the consecutive reaction of
Me3SiCtC-NCN-PtCl (10) with Li-2a or Li-2b to give Me3SiCtC-NCN-Pt-CtCR (11a, R ) bipy;
11b, R ) C6H4-4-CtN), which with [n-Bu4N]F produced HCtC-NCN-Pt-CtCR (12a, R ) bipy; 12b,
R ) C6H4-4-CtN). On reacting 12a and 12b with 1, complexes 13a and 13b were formed, which are
highly insoluble, and hence, no further reactions were carried out. The solid state structures of 3a, 3b,
3e, 5b, 5c, and 16a are reported. Most characteristic for these complexes is that the appropriate transition
metals are linked by carbon-rich organic bridging units. The electrochemical properties of selected samples
(3a-3c, 5a-5c, 7, 9, 16a, and 16b) are reported. The cyclovoltammetric data show that there is no
significant influence of the organic and organometallic acetylide units on the redox potential of the
diphenylphosphino ferrocene in 3a- 3c and 5a-5c. Remarkable is that the chelate coordination of the
bipyridyl unit to Cu(I) in 16a results in a reduction of Cu(I) followed by reoxidation of Cu(0) without
any structural change of the molecule involved, which is unique in titanium(IV)-copper(I) chemistry.
incorporation into more complex structures, ferrocene has
become an excellent building block for the preparation of diverse
organometallic molecules with tailor-made properties.3 In this
respect, ferrocenyl moieties could successfully be introduced
in heteromultimetallic coordination complex chemistry by using
the molecular, modular “Tinkertoy” approach.4 This concept
allows the specific building design of new types of complexes
with novel and, hence, unique chemical and physical properties.4
Another extensively investigated building block in the
synthesis of higher nuclear rigid-rod structured compounds is
gold(I) phosphine acetylide (R3P)Au-CtCR (R ) singly bonded
organic or organometallic group), since such species have
attracted growing attention due to their rich luminescence
properties and their ability to build supramolecular structures
based on the aurophilic nature of gold.5
Introduction
In recent years, the chemistry of organometallic complexes
in which transition metals are spanned by organic and/or
inorganic bridging units was intensively studied in regard to
their novel structural, spectroscopic, and photophysical proper-
ties.1,2 For example, employing alkynyls as linking groups
between transition metal atoms allowed the synthesis of diverse
rigid-rod structured assemblies with redox-active metal-organic
or organometallic complex termini, e.g. functionalized fer-
rocenes.1 Due to its robustness, electron richness, redox proper-
ties, and the well-established synthesis methodologies for its
* To whom correspondence should be addressed. E-mail: heinrich.lang@
chemie.tu-chemnitz.de.
10.1021/om701021y CCC: $40.75
2008 American Chemical Society
Publication on Web 02/22/2008

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1215
Scheme 1
In the context of this background, herein we report the
synthesis, reaction chemistry, structure, and electrochemical
behavior of diphenylphosphinoferrocene-coordinated gold(I)
acetylides.
Results and Discussion
The diphenylphosphinoferrocene gold(I) acetylides Fc-PPh2-
Au-CtCR (3a, R ) bipy; 3b, R ) C6H4-4-CtN; 3c, R )
C5H4N-4; 3d, R ) NCN-H; 3e, R ) NCN-I; Fc ) (η5-C5H5)(η5-
C5H4)Fe; bipy ) 2,2′-bipyridyl-5-yl; NCN ) [C6H2(CH2NMe2)2-
2,6]-) were prepared from the reaction of their chloro precursor
Fc-PPh2-AuCl (1) with terminal alkynes HCtCR (2a, R ) bipy;
2b, R ) C6H4-4-CtN; 2c, R ) C5H4N-4) in the presence of
[CuI] in diethyl amine at 25 °C (Scheme 1).5a However, this
method is limited to the preparation of 3a-3c. Treatment of 1
with HCtCR (2d, R ) NCN-H; 2e, R ) NCN-I) admittedly
gave the desired complexes 3d and 3e in very low yield, but
these compounds could not be separated from the unreacted
starting materials, and hence, another synthesis route had to be
developed. Reacting 1 with a 50% excess of the lithium
acetylides Li-2d and Li-2e in diethyl ether at low temperature
resulted in the formation of yellow 3d and 3e, which, after
Scheme 2
appropriate workup, could be isolated in good yield (Experi-
mental Section).
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The synthesis strategy used in the preparation of 3a-3c
(Scheme 1) could successfully be transferred to organometallic
alkynes of type HCtC-MLn (4a, MLn ) (η6-C6H5)Cr(CO)3;
4b, MLn ) Fc; 4c, MLn ) Rc; Rc ) (η5-C5H5)(η5-C5H4)Ru),
as shown in Scheme 2. Reacting the gold(I) chloride 1 with
4a-4c gave the heterotrimetallic Fe-Au-M system FcPPh2Au-
CtCMLn (5a, MLn ) (η6-C6H5)Cr(CO)3; 5b, MLn ) Fc; 5c,
MLn ) Rc), in which three different transition metal atoms are
connected by carbon-rich bridging units. After column chro-
matography these compounds were isolated as orange solid
materials (Experimental Section).
Compounds 3a-3e and 5a-5c are soluble in organic solvents
such as diethyl ether, tetrahydrofuran, dichloromethane, and
toluene. While solutions containing 5a rapidly turn green after
exposure to air, due to oxidation processes, all other heterobi-
and heterotrimetallic compounds are stable.
All newly synthesized complexes gave satisfactory elemental
analyses and have been fully characterized by IR and NMR
spectroscopy (1H, 13C{1H}, 31P{1H}). The solid state structures
of 3a, 3b, 3e, 5b, and 5c were determined by single-crystal
X-ray structure analysis.
The IR spectra of 3 and 5 display a characteristic absorption
band for the CtC unit at ca. 2120 cm-1, which is almost not
influenced by the organic or organometallic groups R or MLn.
Further typical vibrations are found at 2225 cm-1 for the cyano
unit in 3b and at 1883 and 1963 cm-1 for the carbonyl ligands
in 5a.6,7
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2005, 24, 4198. (h) Long, N. J. Angew. Chem., Int. Ed. 1995, 34, 21. (i)
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1216 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
Table 1. Selected Bond Distances and Angles for 3a, 3b, 3e, 5b, and 5c
3a
3b
Bond Distances (Å)
3e
5b
5c
P1-Au1
2.2792(9)
2.051(4)
1.128(6)
1.462(5)
1.6551(2)
1.6377(2)
2.2715(8)
1.995(3)
1.192(5)
1.429(5)
1.6453(1)
1.6572(1)
2.2716(13)
1.993(5)
1.181(7)
1.454(7)
1.6489(3)
1.6321(3)
2.2653(8)
2.010(3)
1.177(5)
1.416(5)
1.6311(2)
1.6561(2)
1.6367(1)
1.6431(1)
2.2719(11)
1.999(5)
1.189(5)
Au1-C23
C23-C24
C24-C25
1.429(6)
a
Fe1-D1
Fe1-D2
1.6337(2)
1.6482(2)
1.8024(1)
1.8053(2)
b
c
Fe2(Ru1)-D3
Fe2(Ru1)-D4
C28-I1
d
2.111(5)
C31-N1
1.131(5)
Angles (deg)
P1-Au1-C23
Au1-C23-C24
C23-C24-C25
176.79(10)
175.4(4)
175.5(5)
177.88(12)
175.1(3)
175.8(4)
177.23(15)
178.6(5)
176.8(6)
178.07(10)
170.6(3)
176.4(4)
178.59(13)
173.3(4)
175.9(5)
a D1 ) centroid of C5H4 at Fe1. b D2 ) centroid of C5H5 at Fe1. c D3 ) centroid of C5H4 at Fe2 (Ru1). d D4 ) centroid of C5H5 at Fe2 (Ru1).
Table 2. Electrochemical Data of 3a-3c, 5a-5c, 7, 9, 16a, and 16ba
Reduction
Oxidation
compd
bipy/bipy- E0 (∆Ep)
-2.69 (0.23)b
M(I)/M(0) Ep,red/E0 (∆Ep)
Ti(IV)/Ti(III) E0 (∆Ep)
Fe(II)/Fe(III) E0 (∆Ep)
Mn/Mn+1 Ep,ox/E0 (∆Ep)
3a
0.305 (0.10)
0.28 (0.135)b
0.31 (0.105)
0.31 (0.10)
0.325 (0.18)
0.32 (0.10)
0.35 (0.12)
0.31 (0.10)
0.28 (0.115)
0.27 (0.115)
3b
3c
5a
5b
5c
7
0.56c
-0.005 (0.10)d
0.30e
-0.245 (0.085)e
9b
-1.30f
-1.80 (0.18)h
-1.635 (0.18)
-1.76 (0.18)h
-1.75 (0.16)h
16ab
-2.72 (0.16)
-2.71 (0.18)
-1.41 (0.115)f
16bb
-1.30g
0.27 (0.12)
a Cyclic voltammograms from 10-3 M solutions in dichloromethane at 25 °C with [n-Bu4N]PF6 (0.1 M) as supporting electrolyte, scan rate ) 0.10
V · s-1. All potentials are given in V and are referenced to the FcH/FcH+ redox couple (FcH ) (η5-C5H5)2Fe) with E0 ) 0.00 V (∆Ep ) 0.10 V)).20,21
b In tetrahydrofuran. c Mn ) Cr(0). d Mn ) Fe(II). e Mn ) Ru(II). f M ) Cu. g M ) Ag. h From [Ti](CtCSiMe3)2.
The 31P{1H} NMR spectra of 3 and 5 show one singlet at
ca. 36 ppm, which is, compared to 1 (27.6 ppm),5dshifted by 8
ppm to lower field. This can be used to monitor the progress
of the reaction of 1 with 2 or 4. The chemical shift of this
group is thereby not dependent on the nature of R.
Single crystals of 3a, 3b, 3e, 5b, and 5c suitable for X-ray
diffraction studies could be grown by slow vapor diffusion of
petroleum ether into a dichloromethane solution of the respective
transition metal complexes at room temperature. The solid state
structures of 3a, 3b, 3e, 5b, and 5c are shown in Figures 1–5.
Their bond distances (Å) and angles (deg) are given in Table
1. The crystal and structure refinement data are summarized in
Table 3 (3a, 3b, and 3e) and Table 4 (5b, 5c) (Experimental
Section).
The overall structural features of 3a, 3b, 3e, 5b, and 5c are
similar to those of related structurally characterized diphe-
nylphosphinoferrocene- and phosphine-gold(I) acetylide-
containing compounds with gold in an essentially linear
arrangement (P1-Au1-C23-C24) (Figures 1–5, Table 1).5 The
cyclopentadienyl rings of the ferrocene and ruthenocene (5c)
entities, respectively, are rotated by 3.13(3)° (3a), 7.66(1)° (3b),
9.90(6)° (3e), 9.86(4)° and 7.16(6)° (5b), as well as 9.29(6)°
and 9.74(1)° (5c) to each other, which verifies an almost eclipsed
conformation. The distance of the CtC bond that is attached
to gold(I) is for the bipyridyl-substituted species 3a 1.128(6)
Å, while in all other molecules this separation is found between
1.177(5) and 1.192(5) Å (Table 1). All other bond distances
and angles require no further discussion, because they agree
well with those parameters described for related transition metal
complexes.5 The torsion angle between the two pyridine rings
of the bipyridyl unit in 3a is 18.8(6)°, indicating the nonplanarity
of this building block (Figure 1).
1
The H and 13C{1H} NMR spectra of all complexes show
resonance signals and coupling patterns that are consistent with
their proposed structures (Experimental Section). In all cases,
no residual signals attributable to acetylenic hydrogens were
observed in the 1H NMR spectra of 3 and 5, proving that in the
synthesis of these complexes the substitution of acetylenic
protons by the corresponding gold(I) fragment has been
quantitative. In the 13C{1H} NMR spectra of 3a-3e a resonance
signal at 102–105 ppm is observed which can be assigned to
one of the sp-hybridized acetylide carbon atoms at gold(I).
Nevertheless for 5a-5c such a signal could not be detected.
However, due to the fact that only for 3e a splitting of this signal
into a doublet is observed, we cannot unequivocally assign this
resonance. Most representative for 1, 3, and 5, compared to the
starting material diphenylphosphinoferrocene, is the increase of
their C6H5 and C5H4 JCP coupling constants as a result of the
phosphorus coordination to gold(I) (Experimental Section).5
(6) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
Coordination Compounds, 4th ed.; John Wiley and Sons:New York, 1986,
and literature cited therein.
(7) (a) Hong, F. E.; Lo, S. C.; Liou, M. W.; Chang, Y. T.; Lin, C. C. J.
Organomet. Chem. 1996, 506, 101. (b) Müller, T. J. J.; Ansorge, M.;
Lindner, H. J. Chem. Ber. 1996, 129, 1433. (c) Müller, T. J. J.; Lindner,
H. J. Chem. Ber. 1996, 129, 607.
The pendant nitrogen-containing mono- and bidentate ligands
in 3a-3e should be able to coordinate to different transition

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1217
Table 3. Crystal and Intensity Collection Data for 3a, 3b, and 3e
3a 3b
3e
fw
831.28
693.29
908.36
chemical formula
cryst syst
space group
a (Å)
b (Å)
c (Å)
C35H28AuCl2FeN2P
triclinic
P1
C31H23AuFeNP
monoclinic
C2/c
C36H37AuFeIN2P
monoclinic
P2(1)/c
j
9.0155(10)
13.2674(15)
14.0530(16)
89.565(2)
85.665(2)
72.289(2)
1596.5(3)
1.729
25.095(2)
9.5949(8)
21.9949(14)
90.014(6)
102.725(6)
89.967(7)
5166.0(7)
1.783
8.993(2)
12.464(3)
31.133(8)
90
90.645(5)
90
3489.5(16)
1.729
1760
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
Fcalc (g cm-3
F(000)
)
812
2688
cryst dimens (mm3)
Z
0.3 × 0.3 × 0.2
0.3 × 0.2 × 0.1
0.4 × 0.3 × 0.2
2
8
4
max., min. transmn
absorp coeff (µ, mm-1
scan range (deg)
index ranges
0.9999, 0.48753
5.289
25.9997, 2.8406
6.317
0.99999, 0.65829
5.572
)
1.45 to 28.31
-11 e h e 12
-17 e k e 17
0 e l e 18
19 287
2.85 to 26.07
-31 e h ′ 31
-11 e k e 11
-27 e l e 27
24 146
1.76 to 26.44
-11 e h e 11
0 e k e 15
0 e l e 38
40 100
total no. of reflns
no. of unique reflns
R(int)
7765
0.0352
5108
0.0261
7521
0.0354
no. of data/restraints/params
goodness-of-fit on F2
R1,a wR2a [I g 2σ(I)]
R1,a wR2a (all data)
7765/0/379
1.011
0.0352, 0.0839
0.0436, 0.0883
1.068, -1.172
5108/0/316
0.989
0.0235, 0.0486
0.0454, 0.0519
0.731, -0.277
7168/87/413
1.049
0.0344, 0.0861
0.0453, 0.0930
1.407, -1.468
max., min. peak in final
Fourier map (e Å-3
)
2
2 2
2
2 2
a R1 ) [∑(4Fo| - |Fc|)/∑|Fo|); wR2 ) [∑(w(Fo - Fc ) )/∑(wFo4)]1/2. S ) [∑w(Fo - Fc ) ]/(n - p)1/2. n ) number of reflections, p ) parameters
used.
Table 4. Crystal and Intensity Collection Data for 5b, 5c, and 16a
5b 5c
16a
fw
776.20
821.42
1501.33
chemical formula
cryst syst
space group
a (Å)
b (Å)
c (Å)
C34H28AuFe2P
triclinic
P1
C34H28AuFePRu
triclinic
P1
C60H70AuCuF6FeN2P2Si4Ti
triclinic
P1
16.9879(8)
21.3635(11)
22.9555(11)
98.8570(10)
95.7660(10)
105.0720(10)
7861.9(7)
j
j
j
7.9659(6)
12.0238(10)
15.1400(13)
100.165(7)
94.558(7)
96.371(7)
1411.2(2)
1.827
8.2561(8)
11.9946(14)
14.9913(19)
99.395(10)
93.651(9)
96.474(9)
1450.2(3)
1.881
R (deg)
ꢀ (deg)
γ (deg)
V (Å3)
Fcalc (g cm-3
F(000)
)
1.268
3017
756
792
cryst dimens (mm3)
Z
0.5 × 0.4 × 0.1
0.3 × 0.2 × 0.1
0.3 × 0.06 × 0.05
2
2
4
max., min. transmn
absorp coeff (µ, mm-1
scan range (deg)
index ranges
1.56047, 0.27804
6.278
1.10872, 0.74670
6.130
0.99999, 0.62478
2.579
)
2.93 to 26.11
-9 e h e 9
-14 e k e 14
-18 e l e 18
13 338
2.85 to 26.00
-10 e h e 10
-14 e k e 14
-18 e l e 18
14 629
0.91 to 26.41
-21 e h e 21
-26 e k e 26
0 e l e 28
69 529
total no. of reflns
no. of unique reflns
R(int)
5535
0.0227
5703
0.0328
32 186
0.0819
no. of data/restraints/params
5535/0/343
0.999
0.0231, 0.0535
0.0316, 0.0558
0.628, -0.715
5703/0/343
0.823
0.0258, 0.0449
0.0560, 0.0476
0.667, -0.854
32186/109/1465
1.028
0.0742, 0.2056
0.1488, 0.2472
1.888, -1.128
goodness-of-fit on F2
3
R1,a wR2a [I 2σ(I)]
R1,a wR2a (all data)
max., min. peak in final
Fourier map (e Å-3
)
a R1 ) [∑(4Fo| - |Fc|)/∑|Fo|); wR2 ) [∑(w(Fo - Fc ) )/∑(wFo4)]1/2. S ) [∑w(Fo - Fc ) ]/(n - p)1/2. n ) number of reflections, p ) parameters
used.
2
2 2
2
2 2
metal fragments and consequently should be suitable for the
when 3b was treated with the metal–carbonyl W(CO)5(thf), the
phosphorus-gold bond was cleaved to form FcPPh2W(CO)5.8
A similar behavior was observed for 3c. A further product could
not be characterized and probably results from decomposition.
construction of transition metal assemblies of higher nuclearity.
Thus, these complexes were reacted with different transition
metal sources, of which not all were successful. For example,

1218 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
Figure 4. ORTEP (50% ellipsoid probability level) of 5b with the
atom-numbering scheme (the hydrogen atoms are omitted for
clarity).
Figure 1. ORTEP (50% ellipsoid probability level) of 3a with the
atom-numbering scheme (the hydrogen atoms and one molecule
of dichloromethane are omitted for clarity).
Figure 5. ORTEP (50% ellipsoid probability level) of 5c with the
atom-numbering scheme (the hydrogen atoms are omitted for
clarity).
Figure 2. ORTEP (50% ellipsoid probability level) of 3b with the
atom-numbering scheme (the hydrogen atoms are omitted for
clarity).
solution from yellow to intense red. Monitoring the progress
of the reaction was also possible by following the shift of the
νCtN vibration from 2225 in 3b to 2199 in 7, which is a rather
unusual shift for η1-bonded nitriles and points to a CtN bond
weakening, due to the back-bonding properties of the coordi-
nated [Ru] fragment.6,10
Also complex 3c should permit the synthesis of heteromul-
timetallic systems. The capability of the pyridine entity to
coordinate to further transition metal building blocks was proven
by its reaction with the bis(alkynyl) titanocene-copper(I)
complex {[Ti](µ-σ,π-CtCSiMe3)2}CuOTf (8a). Performing this
reaction in diethyl ether as the solvent, the desired product
precipitated and could be isolated as a shiny golden solid in
Figure 3. ORTEP (50% ellipsoid probability level) of 3e with the
atom-numbering scheme (the hydrogen atoms are omitted for
clarity).
When 3b is treated with the dinitrogen-bridged diruthenium
(8) (a) Kotz, J. C.; Nivert, C. L.; Lieber, J. M.; Reed, R. C. J. Organomet.
Chem. 1975, 91, 87. (b) Kotz, J. C.; Nivert, C. L. J. Organomet. Chem.
1973, 52, 387.
complex [Ru]NtN[Ru] (6) ([Ru]
)
[η3-mer-{2,6-
(Me2NCH2)2C5H3N}RuCl2]),9 the formation of neutral hetero-
trimetallic 7 occurs by liberation of N2. The reaction could be
followed visually by the change of the color of the reaction
(9) Abbenhuis, R. A. T. M.; del Río, I.; Bergshoef, M. M.; Boersma,
J.; Veldman, N.; Spek, A. L.; van Koten, G. Inorg. Chem. 1998, 37, 1749.
(10) Storhoff, B. N.; Lewis, H. C. Coord. Chem. ReV. 1977, 23, 1.

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1219
Scheme 3. Synthesis of 13a and 13ba
good yield. In [FcPPh2Au-CtC-C5H4N-Cu{(Me3SiCtC)2-
[Ti]}]OTf (9) the metals gold, copper, and titanium are brought
in close proximity to each other in a linear fashion. The
formation of tetrametallic 9 was evidenced by IR spectroscopy.
Upon coordination of the pyridine donor group to copper(I) both
CtC vibrations, as well at titanium as at gold, are influenced.
Compared to 8a (1924 cm )
-1 11 the νCtCTi frequency is shifted
to lower wavenumbers and is found at 1915 cm-1 (9), while
the νCtCAu vibration at gold is shifted somewhat to higher
wavenumbers due to coordination to copper (Experimental
Section).
n
a
(i) LiCtCR, Et2O, -80 – 25 °C; (ii) [ Bu4N]F, CH2Cl2, 25 °C;
(iii) FcPPh2AuCl (1), [CuI], Thf, HNEt2, 25 °C.
Scheme 4. Synthesis of 15, 16a and 16b.a
The identity of heterotrimetallic 7 and heterotetrametallic 9
was additionally evidenced from mass spectrometric investiga-
tions. The electrospray ionization mass spectra (ESI-MS) show
the molecular ion peaks at m/z ) 1058.2 [M]+ (7) and 1248.2
[M - CF3SO3]+ (9), whose mass and isotope distribution pattern
are in agreement with the formulated structures.
The standard procedure involving lithiation-trans-metalation
for the synthesis of platinum-NCN pincers12 from 3d and 3e
could not be applied for the preparation of FcPPh2Au-CtC-4-
NCN-PtCl, a compound that would enable one to anchor further
N-ligating sites to the platinum atom via an acetylide bridging
unit. Our results showed that the introduction of a PtCl entity
to a NCN pincer unit was unsuccessful since competitive
reactions occur. Oxidative addition of the C-I bond to pal-
ladium(0) by reacting 3e with [Pd2(dba)3(CHCl3)] (dba )
dibenzylidene acetone) in benzene also did not give the
respective Fe-Au-Pd complex.13 Instead, reaction mixtures were
obtained from which no unequivocally characterizable com-
pounds could be separated. Refluxing 3e with half an equivalent
of [Pt(tol)2(SEt2)]2 (tol ) 4-tolyl) in toluene as solvent also did
not give the desired Fe-Au-Pt product.13 Thus, we had to choose
another synthetic way to prepare FcPPh2Au-CtC-NCN-Pt-
CtC-R (13a, R ) bipy; 13b, R ) C6H4-4-CtN). A straight-
forward synthesis procedure for the latter molecules is outlined
in Scheme 3.
a
(i) (nbd)Mo(CO)4 (14) CH2Cl2/Thf, 25 °C; (ii) {[Ti](µ-σ,π-
CtCSiMe3)2}MX (8b, M ) Cu(NtCMe), X ) PF6; 8c, M ) Ag, X
) OClO3), Thf, 25 °C.
12b, R ) C6H4-4-CtN) was obtained only in low yield, which
is attributed to the workup method applied (Experimental
Section). Addition of FcPPh2AuCl (1) to 12a and 12b, respec-
tively, under similar reaction conditions as already described
for the preparation of 3a-3c, afforded the appropriate FcPPh2Au-
CtC-NCN-Pt-CtCR complexes 13a and 13b (Scheme 3).
Notable is that due to the low solubility of 13a and 13b, even
in polar organic solvents, full characterization of these species
was not possible (Experimental Section). Consequently, we did
not carry out any further reaction with these species.
The reaction of Me3SiCtC-NCN-PtCl (10) with Li-2a or
Li-2b in diethyl ether at ambient temperature gave Me3SiCtC-
NCN-Pt-CtCR (11a, R ) bipy; 11b, R ) C6H4-CtN).14
Desilylation of 11a and 11b was achieved by addition of
tetrabutyl ammonium fluoride in dichloromethane at room
temperature. However, HCtC-NCN-Pt-CtCR (12a, R ) bipy;
Another molecule with a multifunctional ligand allowing to
introduce further metal-containing building blocks is FcPPh2Au-
CtC-bipy (3a) as outlined earlier. Thus, complex 3a was
reacted with 1 equiv of (nbd)Mo(CO)4 (14) in a 1:5 mixture of
tetrahydrofuran/dichloromethane at room temperature. Replace-
ment of nbd by the better donor–acceptor component 2,2′-
bipyridyl gave trimetallic FcPPh2Au-CtC-bipy[Mo(CO)4] (15)
in 78% yield (Scheme 4). When instead of 14 the organometallic
π-tweezer molecule {[Ti](µ-σ,π-CtCSiMe3)2}MX (8b, M )
Cu(NtCMe), X ) PF6; 8c, M ) Ag, X ) OClO3) was reacted
with 3a, then heterotetrametallic [FcPPh2Au-CtCbipy({[Ti](µ-
σ,π-CtCSiMe3)2}M)]X (16a, M ) Cu, X ) PF6; 16b, M )
Ag, X ) ClO4) could be isolated as a red crystalline solid in
excellent yield (Scheme 4).15 In 15, 16a, and 16b different
(11) Janssen, M. D.; Herres, M.; Zsolnai, L.; Spek, A. L.; Grove, D. M.;
Lang, H.; van Koten, G. Inorg. Chem. 1996, 35, 2476.
(12) (a) Grove, D. M.; van Koten, G.; Louwen, J. N.; Noltes, J. G.;
Spek, A. L.; Ubbels, H. J. C. J. Am. Chem. Soc. 1982, 104, 6609. (b)
Lagunas, M. C.; Gossage, R. A.; Spek, A. L.; van Koten, G. Organometallics
1998, 17, 731.
(13) Köcher, S.; Walfort, B.; van Klink, G. P. M.; van Koten, G.; Lang,
H. J. Organomet. Chem. 2006, 691, 3955.
(14) Back, S.; Gossage, R. A.; Lang, H.; van Koten, G. Eur. J. Inorg.
Chem. 2000, 1457.

1220 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
transition metals such as Fe, Au, Mo, Cu, Ag, and Ti are bridged
by carbon-rich connecting units. These complexes are astonish-
ingly stable in the solid state; that is, no intramolecular redox
processes are observed. In solution, however, they slowly
decompose to yield materials that are insoluble in organic
solvents. An exception is complex 16b. This molecule decom-
poses in solution to produce elemental silver and the free
organometallic π-tweezer molecule [Ti](CtCSiMe3)2 together
with 3a.16
alkynyl unit that is attached to gold(I) is 1.191(12) (molecule
A) and 1.219(13) Å (molecule B), respectively (Figure 6). All
other bond separations and angles require no further discussion
because they agree well with those parameters described for
related transition metal complexes.5 The bipyridyl building block
chelates via the nitrogen atoms N1 and N2 to Cu1 (molecule
A) or N3 and N4 to Cu2 (molecule B), thus resulting in a
pseudotetrahedral coordination at copper(I). The structural
features of the heterobimetallic organometallic π-tweezer unit
[{[Ti](µ-σ,π-CtCSiMe3)2}Cu]+ are in accordance with this type
of molecule.16,17 The torsion angles between the two pyridine
rings of the bipyridyl unit are 3.87(6)° (molecule A) (rms
deviation 0.0341°) and 1.70(6)° (molecule B) (rms deviation
0.0179°), indicating the planarity of this building block (Figure
6). The dihedral angle formed by the calculated mean planes I
(N1, N2, C28, C29, C30 and C31) and II (Ti1, C35, C36, C40
and C41) is 85.45(2)° (rms deviation of fitted atoms ) 0.0284
(plane I) and 0.0246 Å (plane II)) for molecule A and mean
planes III (N3, N4, C88, C89, C90 and C91) and IV (Ti2, C95,
C96, C100 and C101) is 89.89(2)° (rms deviation of fitted atoms
) 0.0137 (plane III) and 0.0411 Å (plane IV)) for molecule B.
Both the bipyridyl moiety and the π-tweezer unit ([Ti]-
(CtCSiMe3)2) coordinate copper in plane.
Complexes 15, 16a, and 16b gave satisfactory elemental
1
analysis and have been characterized by IR and H, 13C{1H}
(with the exception of 16b), and 31P{1H} NMR spectroscopy.
The identity of tetrametallic 16a was further confirmed by a
single-crystal X-ray diffraction study (see below).
The IR spectra of 15, 16a, and 16b show, as do complexes
3 and 5, characteristic νCtC absorptions for the Au-CtC and
Ti-CtC fragments at ca. 2118 and 1924 (16a) or 1952 cm-1
(16b).5,16,17 Consistent with the structure of 15, the IR spectra
of this molecule present in the carbonyl region, as expected for
this type of metal–carbonyl entity, four strong CO vibrations
between 1829 and 2011 cm-1 (Experimental Section).18
The 1H and 13C{1H} NMR spectra of 15, 16a, and 16b show
representative chemical shifts for the organic building blocks
(Experimental Section). Noteworthy to mention in the 1H NMR
spectra of 16a and 16b, when compared with 8b and 8c, is the
highfield shift of the Me3SiCtC protons from ca. 0.20 ppm
(8b, 8c)17 to -0.49 (16a) or -0.30 ppm (16b), which can be
explained by the ring current of the chelating bipyridyl ligand.
Furthermore, heterotetrametallic 16a shows two separated
singlets for the Me3Si protons of the titanium-coordinated
cyclopentadienyl ligands, which is attributed to their unsym-
metrical chemical environment. These observations prove the
successful formation of multimetallic 15, 16a, and 16b.16
The 31P{1H} NMR spectra of 15, 16a, and 16b show one
typical signal at ca. 36 ppm for the Ph2PAu moiety.5 Addition-
ally, complex 16a, which features a hexafluorophosphate
counterion, possesses a second signal at -145 ppm splitting
into a septet due to JPF coupling (1JPF ) 713 Hz).
Electrochemistry. Complexes 3a-3c, 5a-5c, 7, 9, 16a, and
16b were subjected to cyclovoltammetric studies. The electro-
chemical data are summarized in Table 2. The Fe(II)/Fe(III)
redox potentials of the FcPPh2 units are almost not influenced
by the nature of R of the acetylenic ligands CtCR. The values
show that, compared to FcPPh2 (E0 ) 0.09 V, ∆Ep ) 0.15 V),8a
a decreased electron density at Fe(II) in 3a-3c and 5a-5c is
characteristic; that is, these species are more difficult to oxidize,
which can be explained by the electron-withdrawing effect of
the respective Au(I) moieties. Nevertheless, a gold(I) reduction
could not be observed, either in dichloromethane or in tetrahy-
drofuran solutions for all newly synthesized compounds.5d The
reduction of the bipyridyl entity in 3a is only observed in
tetrahydrofuran, enabling the measurement to be carried out into
a more negative region and is found at E0 ) -2.69 V (∆Ep )
0.23 V).19
The solid state structure of 16a was determined by single-
crystal X-ray structure analysis (Figure 6). Complex 16a
The cyclic voltammograms of complexes 5a-5c show
additional oxidation processes in the anodic region which can
be assigned to the appropriate MLn building blocks. Compound
5b depicts a further reversible Fe(II)/Fe(III) oxidation issuing
from the ethynyl ferrocene unit (Figure 7), while the oxidation
processes of ruthenium(II) (5c) and chromium(0) (5a) are found
to be irreversible (Table 2).
j
crystallizes in the triclinic space group P1. The asymmetric unit
cell contains two crystallographically independent molecules,
which are shown in Figure 6. Selected bond distances (Å) and
angles (deg) are presented in the legend of Figure 6. The crystal
and structure refinement data are summarized in Table 4
(Experimental Section).
Heterotetranuclear 16a contains the transition metals gold,
copper, iron, and titanium, whereby Au1 is two-coordinated,
Fe1 is part of a sandwich structure, and Cu1 and Ti1 possess
pseudotetrahedral environments (Figure 6). A linear one-
dimensional P1-Au1-C23-C24-C26 arrangement is set up, which
is typical for phosphine gold(I) acetylides.5 The cyclopentadienyl
rings of the ferrocene entity are rotated by 14.00(6)° (molecule
A) and 17.36(9)° (molecule B), respectively, to each other,
which verifies a staggered conformation. The distance of the
The coordination of the nitrile ligand to the [Ru] entity in 7
does not influence the oxidation of the Fc unit (E0 ) 0.31 V,
∆Ep ) 0.10 V) (Figure 8). The Ru(II)/Ru(III) oxidation is
observed at E0 ) -0.245 V (∆Ep ) 0.085 V). Compared to
[Ru]-NtC-C6H5 this process is somewhat shifted to a more
positive potential.22
The electrochemical measurements of all complexes contain-
ing the bis(alkynyl)titanocene building block were carried out
in tetrahydrofuran solutions. The cyclic voltammogram of
(15) Packheiser, R.; Walfort, B.; Lang, H. Jordan J. Chem. 2006, 1,
121.
(19) (a) For free 2,2′-bipyridine see Al-Anber, M.; Vatsadze, S.; Holze,
R.; Thiel, W. R.; Lang, H. J. Chem. Soc., Dalton Trans. 2005, 3632. (b)
Vatsadze, S.; Al-Anber, M.; Thiel, W. R.; Lang, H.; Holze, R. J. Solid
State Electrochem. 2005, 9, 764.
(16) Packheiser, R.; Walfort, B.; Lang, H. Organometallics 2006, 25,
4579.
(17) (a) Lang, H.; George, D. S. A.; Rheinwald, G. Coord. Chem. ReV.
2000, 206–207, 101. (b) Lang, H.; Rheinwald, G. J. Prakt. Chem. 1999,
341, 1. (c) Lang, H.; Köhler, K.; Blau, S. Coord. Chem. ReV. 1995, 143,
113.
(20) Ferrocene/ferrocenium redox couple: Gritzner, G.; Kuta, J. Pure
Appl. Chem. 1984, 56, 461.
(21) A conversion of given electrode potentials to the standard normal
hydrogen electrode is possible: Strehlow, H.; Knoche, W.; Schneider, H.
Ber. Bunsenges. Phys. Chem. 1973, 77, 760.
(18) Herrmann, W. A.; Thiel, W. R.; Kuchler, J. K. Chem. Ber. 1990,
1953.

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1221
Figure 6. ORTEP (30% ellipsoid probability level) of the two crystallographically independent molecules in 16a (molecule A, top; molecule
B, bottom) with the atom-numbering scheme (the hydrogen atoms and the PF6- counterion are omitted for clarity). Selected bond distances
(Å) and angles (deg): Molecule A: P1-Au1, 2.268(2); Au1-C23, 2.007(10); C23-C24, 1.191(12); Cu1-N1, 2.109(7); Cu1-N2, 2.082(7);
Cu1-C35, 2.104(9); Cu1-C36, 2.214(10); Cu1-C40, 2.090(8); Cu1-C41, 2.197(9); Ti1-C35, 2.106(9); Ti1-C40, 2.120(9); C35-C36,
1.234(12); C40-C41, 1.223(12); P1-Au1-C23, 175.7(3); Au1-C23-C24, 174.0(8); C23-C24-C26, 177.7(11); Ti1-C35-C36, 167.5(8);
Ti1-C40-C41, 166.7(7); C35-C36-Si1, 161.8(9); C40-C41-Si2, 162.6(8); Fe1-D1, 1.6349(6); Fe1-D2, 1.6290(5); Ti1-D3, 2.0541(4);
Ti1-D4, 2.0495(4). Molecule B: P2-Au2, 2.275(3); Au2-C83, 1.984(10); C83-C84, 1.219(13); Cu2-N3, 2.131(7); Cu2-N4, 2.079(7);
Cu2-C95, 2.066(9); Cu2-C96, 2.174(9); Cu2-C100, 2.093(8); Cu2-C101, 2.175(9); Ti2-C95, 2.087(9); Ti2-C100, 2.092(9); C95-C96,
1.233(12); C100-C101, 1.244(12); P2-Au2-C83, 175.4(3); Au2-C83-C84, 178.4(10); C83-C84-C86, 176.3(10); Ti2-C95-C96,
166.8(7); Ti2-C100-C101, 165.5(7); C95-C96-Si5, 160.0(9); C100-C101-Si6, 159.9(8); Fe2-D5, 1.6126(8); Fe2-D6, 1.6135(7);
Ti2-D7, 2.0422(4); Ti2-D8, 2.0442(4). (D1, D5 ) centroids of the cyclopentadienyl rings C5H5; D2–4, D6–8 ) centroids of the cyclopentadienyl
rings C5H4).
heterotetrametallic 9 presents next to the Fe(II)/Fe(III) oxidation
at E0 ) 0.28 V (∆Ep ) 0.115 V) an irreversible reduction at
Ep,red ) -1.30 V, which results from the Cu(I)/Cu(0) reduction.
The reduction of copper(I) to copper(0) is typical in Ti-Cu
organometallic π-tweezer chemistry, implying that in such
complexes the reduction occurs initially at the Cu(I) ion,
resulting in fragmentation of the respective complexes.23 Owing
to this, a further reduction wave is observed at E0 ) -1.80 V
(∆Ep ) 0.18 V), which results from the free π-tweezer
[Ti](CtCSiMe3)2 (Ti(IV)/Ti(III)) increasing during multicyclic
experiments, while the Cu(I)/Cu(0) reduction wave disappears.23
Electrochemical studies on 16a show a reversible wave at
0.27 V (∆Ep ) 0.115 V) for the Fc group, similar to 3a (E0 )
0.28 V, ∆Ep ) 0.135 V). A characteristic reversible one-electron
reduction at -2.72 V with ∆Ep ) 0.16 V is additionally found,
which can be assigned to the bipy/bipy- redox couple.19 The
organometallic π-tweezer part in 16a gives rise to two further
one-electron processes. In contrast to 9, in which the copper(I)
ion is monodentate-bonded by a pyridine ligand, the chelate
coordination of the bipyridyl unit to Cu(I) in 16a results in a
reduction of Cu(I) followed by a partial reoxidation of Cu(0)
(E0 ) -1.41 V, ∆Ep ) 0.115 V), presumably without any
structural change of the molecule involved (Figure 9).16 This
is unique in titanium(IV)-copper(I) chemistry. At more negative
potentials two reductions are found resulting from the Ti(IV)/
(22) Back, S.; Gossage, R. A.; Rheinwald, G.; del Río, I.; Lang, H.;
van Koten, G. J. Organomet. Chem. 1999, 582, 126.

1222 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
16a, for the Ti-Ag tweezer part an irreversible wave at Ep,red
)
-1.30 V for Ag(I) is characteristic; that is, no reoxidation peak
is observed. Presumably reduction of the coinage metal to its
elemental form results in disaggregation of 16b, thus affording
the free organometallic π-tweezer [Ti](CtCSiMe3)2.23 For the
latter species a reduction current peak at Ep,red ) -1.83 V
assigned to the reaction Ti(IV) + e- f Ti(III) is displayed,
together with the corresponding oxidation peak, and a value of
∆Ep ) 0.16 V is calculated. This redox potential is typical for
[Ti](CtCSiMe3)2.23
Conclusion
A series of heterometallic complexes featuring two, three,
or even four different transition metal atoms such as titanium,
molybdenum, iron, platinum, copper, and silver of structural
type FcPPh2Au-CtCR (R ) bipy, C6H4-4-CtN, C5H4N-4,
NCN-H, NCN-I; Fc ) (η5-C5H5)(η5-C5H4)Fe; bipy ) 2,2′-
bipyridyl-5-yl; NCN ) [C6H2(CH2NMe2)2-2,6]-), FcPPh2Au-
Figure 7. Cyclic voltammogram (anodic region) of 5b (10-3
M
solution in dichloromethane at 25 °C with [n-Bu4N]PF6 (0.1 M) as
supporting electrolyte, scan rate ) 0.10 V · s-1). All potentials are
referenced to the FcH/FcH+ redox couple (FcH ) (η5-C5H5)2Fe)
with E0 ) 0.00 V (∆Ep ) 0.10 V)).20,21
CtCMLn (MLn
) )
(η6-C6H5)Cr(CO)3, Fc, Rc; Rc
(η5-C5H5)(η5-C5H4)Ru), FcPPh2Au-CtC-C6H4-4-CtN-[Ru],
[FcPPh2Au-CtC-C5H4N-Cu{(Me3SiCtC)2[Ti]}]OTf, FcPPh2Au-
CtC-NCN-Pt-CtCR (R ) bipy, C6H4-CtN), FcPPh2Au-
CtCbipy[Mo(CO)4], and [FcPPh2Au-CtCbipy({[Ti](µ-σ,π-
CtCSiMe3)2}M)])X (M ) Cu, X ) PF6; M ) Ag, X ) ClO4)
have been synthesized in straightforward consecutive synthesis
procedures. In these molecules the appropriate transition metals
are spanned by carbon-rich connectivities based on alkynyls,
and hence, they enrich the so far only scarcely described class
of multimetallic organometallic compounds featuring different
early and late transition metal atoms. These complexes have
been subjected to cyclovoltammetric studies, showing redox
processes attributed to the relevant metal centers. The influence
of the metal atoms on each other has thereby turned out to be
relatively tenuous. Noteworthy is that in [FcPPh2Au-
CtCbipy({[Ti](µ-σ,π-CtCSiMe3)2}Cu)]PF6 the chelate coor-
dination of the bipyridyl unit to Cu(I) results in a reduction of
Cu(I) followed by reoxidation of Cu(0) presumably without any
structural change of the molecule involved, which is unique in
titanium(IV)-copper(I) chemistry.
Figure 8. Cyclic voltammogram (anodic region) of 7 (10-3
M
solution in dichloromethane at 25 °C with [n-Bu4N]PF6 (0.1 M) as
supporting electrolyte, scan rate ) 0.10 V · s-1). All potentials are
referenced to the FcH/FcH+ redox couple (FcH ) (η5-C5H5)2Fe)
with E0 ) 0.00 V (∆Ep ) 0.10 V).20,21
Experimental Section
General Data. All reactions were carried out under an atmo-
sphere of nitrogen using standard Schlenk techniques. Tetrahydro-
furan, diethyl ether, petroleum ether, n-hexane, and n-pentane were
purified by distillation from sodium/benzophenone ketyl; dichlo-
romethane was purified by distillation from calcium hydride. Celite
(purified and annealed, Erg. B.6, Riedel de Haen) was used for
filtrations.
Instruments. Infrared spectra were recorded with a Perkin-Elmer
FT-IR spectrometer Spectrum 1000. 1H NMR spectra were recorded
with a Bruker Avance 250 spectrometer operating at 250.130 MHz
in the Fourier transform mode; 13C{1H} NMR spectra were
recorded at 62.860 MHz. Chemical shifts are reported in δ (parts
per million) downfield from tetramethylsilane with the solvent as
reference signal (1H NMR: CDCl3, δ ) 7.26; 13C{1H} NMR:
CDCl3, δ ) 77.16).24 31P{1H} NMR spectra were recorded at
101.255 MHz in CDCl3 with P(OMe)3 as external standard (δ )
139.0, relative to H3PO4 (85%) with δ ) 0.00 ppm). ESI-TOF mass
spectra were recorded using a Mariner biospectrometry workstation
Figure 9. Cyclic voltammogram (cathodic region) of 16a (10-3
M solution in tetrahydrofuran at 25 °C with [n-Bu4N]PF6 (0.1 M)
as supporting electrolyte, scan rate ) 0.10 V · s-1). All potentials
are referenced to the FcH/FcH+ redox couple (FcH ) (η5-C5H5)2Fe)
with E0 ) 0.00 V (∆Ep ) 0.10 V).20,21
Ti(III) redox couple of intact 16a (E0 ) -1.635 V, ∆Ep ) 0.18
V) and the free tweezer molecule [Ti](CtCSiMe3)2 (E0
-1.76 V, ∆Ep ) 0.18 V) (Figure 9).
)
23
(23) Stein, T.; Lang, H.; Holze, R. J. Electroanal. Chem. 2002, 520,
163, and references therein.
In contrast to 16a, tetrametallic 16b shows a somewhat
different electrochemical behavior. While the Fc and bipy
moieties behave in the same manner as discussed earlier for
(24) Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997,
62, 7512.

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1223
5
4
4.0 (Applied Biosystems). Cyclic voltammograms were recorded
in a dried cell purged with purified argon. Platinum wires served
as the working electrode and the counter electrode. A saturated
calomel electrode in a separate compartment served as reference
electrode. For ease of comparison, all electrode potentials are
converted using the redox potential of the ferrocene/ferrocenium
couple FcH/FcH+ (FcH ) (η5-C5H5)2Fe, E0 ) 0.00 V) as
reference.20,21 Electrolyte solutions were prepared from tetrahy-
drofuran or dichloromethane and [nBu4N]PF6 (Fluka, dried in oil-
pump vacuum). The appropriate organometallic complexes were
added at c ) 1.0 mM. Cyclic voltammograms were recorded on a
Voltalab 3.1 potentiostat (Radiometer) equipped with a digital
electrochemical analyzer DEA 101 and an electrochemical interface
IMT 102. Microanalyses were performed by the Institute of
Inorganic Chemistry and partly the Institute of Organic Chemistry,
Chemnitz, Technical University.
Hz, JH6′H3′ ) 1 Hz, 1 H, H6′/bipy), 8.83 (dd, JH6H4 ) 2.4 Hz,
5JH6H3 ) 0.6 Hz, 1 H, H6/bipy). 13C{1H} NMR (CDCl3, δ): 68.6
(d, 1JCP ) 64.9 Hz, Ci/C5H4), 70.1 (C5H5), 72.5 (d, 3JCP ) 8.5 Hz,
Cꢀ/C5H4), 73.7 (d, 2JCP ) 13.8 Hz, CR/C5H4), 101.0 (CtC) 120.3
(C3/bipy), 121.3 (C3′/bipy), 122.3 (C5/bipy), 123.6 (C5′/bipy),
128.9 (d, JCP ) 11.2 Hz, Cm/C6H5), 131.3 (d, JCP ) 2.3 Hz,
3
4
Cp/C6H5), 132.1 (d, JCP ) 56.7 Hz, Ci/C6H5), 133.8 (d, JCP
)
1
2
13.8 Hz, Co/C6H5), 136.9 (C4′/bipy), 140.2 (C4/bipy), 149.3 (C6′/
bipy), 152.7 (C6/bipy), 153.4 (C2/bipy), 156.1 (C2′/bipy). 31P{1H}
NMR (CDCl3, 101.249 MHz, δ): 35.95 (s, PPh2). (The second
signal for the CtC entity could not be detected.)
Synthesis of FcPPh2AuCtC-C6H4-4-CtN (3b). To 300 mg
(0.50 mmol) of FcPPh2AuCl (1) dissolved in 50 mL of diethyl
amine were added 80 mg (0.63 mmol) of 4-ethynyl-benzonitrile
(2b) and 1 mg of [CuI]. The resulting turbid reaction mixture was
stirred for 16 h at 25 °C. Afterward all volatiles were removed
under reduced pressure and the remaining solid was subjected to
column chromatography on alumina using toluene as eluent. The
title compound was obtained as an orange solid after evaporation
of the solvent under reduced pressure. Yield: 270 mg (0.39 mmol,
78% based on 1).
Reagents. FcPPh2AuCl (1),5d 5-ethynyl-2,2′-bipyridyl (2a),25
4-ethynylbenzonitrile (2b),26 4-ethynylpyridine (2c),27 HCtC-1-
C6H3(CH2NMe2)2-3,5 (2d),28 I-1-HCtC-4-C6H3(CH2NMe2)2-2,6
(2e),29 (η6-C6H5CtCH)Cr(CO)3 (4a),30 ethynylferrocene (4b),31
ethynylruthenocene (4c),32 [Ru]NtN[Ru] (6),9 Me3Si-CtC-NC-
NPtCl (10),14,33 HCtC-NCNPt-CtC-C6H4CtN (12b),14 (nbd)-
Mo(CO)4, (14),34 {[Ti](µ-σ,π-CtCSiMe3)2}CuOTf (8a),11 [{[Ti](µ-
σ,π-CtCSiMe3)2}Cu(NtCMe)]PF6 (8b),11 and {[Ti](µ-σ,π-
CtCSiMe3)2}AgOClO3 (8c)35 were prepared according to published
procedures. All other chemicals were purchased from commercial
suppliers and were used as received.
Synthesis of FcPPh2AuCtC-bipy (3a). To 150 mg (0.25 mmol)
of FcPPh2AuCl (1) and 50 mg (0.27 mmol) of 5-ethynyl-2,2′-
bipyridyl (2a) dissolved in 50 mL of diethyl amine was added 1
mg of [CuI]. After stirring the reaction solution for 16 h at 25 °C
it was filtered through a pad of Celite and all volatiles were removed
in an oil-pump vacuum. The remaining solid was purified by column
chromatography on silica gel eluting with a diethyl ether/n-hexane
mixture (4:1, v/v). After evaporation of the solvents under reduced
pressure compound 3a was obtained as a yellow solid. Yield: 130
mg (0.17 mmol, 68% based on 1).
Anal. Calc for C31H23NPAuFe (693.3): C, 53.70; H, 3.34; N,
2.02. Found: C, 53.72; H, 3.32; N, 2.04. Mp: 92 °C. IR (KBr,
cm-1): 2225 (s, νCtN), 2116 (m, νAuCtC). H NMR (CDCl3, δ):
1
4.21 (s, 5 H, C5H5), 4.38 (dpt, JHP ) 3.0 Hz, JHH ) 1.8 Hz, 2 H,
HR/C5H4), 4.56 (dpt, JHP ) 1.0 Hz, JHH ) 1.8 Hz, 2 H, Hꢀ/C5H4),
7.42–7.61 (m, 14 H, C6H5 + C6H4). 13C{1H} NMR (CDCl3, δ):
69.8 (d, JCP ) 64.3 Hz, Ci/C5H4), 72.5 (d, JCP ) 8.3 Hz, Cꢀ/
1
3
C5H4), 73.6 (d, JCP ) 13.8 Hz, CR/C5H4), 102.7 (CtC), 109.8
2
(Ci/C6H4), 119.2 (CtN), 128.9 (d, 3JCP ) 11.1 Hz, Cm/C6H5), 130.4
(Ci/C6H4), 131.3 (d, JCP ) 2.1 Hz, Cp/C6H5), 131.9 (CH/C6H4),
4
132.2 (d, JCP ) 54.7 Hz, Ci/C6H5), 132.9 (CH/C6H4), 133.8 (d,
1
2JCP ) 14.0 Hz, Co/C6H5). 31P{1H} NMR (CDCl3, 101.249 MHz,
δ): 36.3 (s, PPh2). (The second signal for the CtC entity could
not be detected.)
Synthesis of FcPPh2AuCtC-C5H4N (3c). To 150 mg (0.25
mmol) of FcPPh2AuCl (1) dissolved in 50 mL of diethyl amine
were added 30 mg (0.29 mmol) of 4-ethynylpyridine (2c) and 1
mg of [CuI]. The resulting turbid reaction mixture was stirred for
16 h at 25 °C. All volatiles were removed under reduced pressure
and the remaining solid was purified by column chromatography
on alumina using a mixture of toluene/tetrahydrofuran (8:1, v/v)
as eluent. After removal of all volatiles in an oil-pump vacuum
compound 3c was obtained as an orange solid. Yield: 100 mg (0.15
mmol, 60% based on 1).
Anal. Calc for C34H26AuFeP (746.13): C, 54.71; H, 3.51; N, 3.75.
Found: C, 55.20; H, 3.69; N, 3.67. Mp: 105 °C. IR (KBr, cm-1):
1
2115 (m, νAuCtC). H NMR (CDCl3, δ): 4.21 (s, 5H, C5H5), 4.39
(dpt, JHP ) 2.8 Hz, JHH ) 1.9 Hz, 2 H, HR/C5H4), 4.55 (dpt, JHP
)
1.0 Hz, JHH ) 1.9 Hz, 2 H, Hꢀ/C5H4), 7.26 (ddd, 3JH5′H4′ ) 7.8 Hz,
4
3JH5′H6′ ) 4.8 Hz, JH5′H3′ ) 1 Hz, 1 H, H5′/bipy), 7.40–7.65 (m,
10 H, C6H5), 7.79 (ddd, 3JH4′H3′ ) 7.8 Hz, 3JH4′H5′ ) 7.8 Hz, 4JH4′H6′
) 1.8 Hz, 1 H, H4′/bipy), 7.92 (dd, 3 JH4H3 ) 8.5 Hz, 4JH4H6 ) 2.4
3
5
Hz, 1 H, H4/bipy), 8.31 (dd, JH3H4 ) 8.5 Hz, JH3H6 ) 0.6 Hz, 1
H, H3/bipy), 8.37 (ddd, 3JH3′H4′ ) 7.8 Hz, 4JH3′H5′ ) 1 Hz, 5JH3′H6′
) 1 Hz, 1 H, H3′/bipy), 8.66 (ddd, 3JH6′H5′ ) 4.8 Hz, 4JH6′H4′ ) 1.8
Anal. Calc for C29H23NPAuFe (669.3): C, 52.04; H, 3.46; N,
2.09. Found: C, 52.35; H, 3.78; N, 2.28. Mp: 196 °C (dec). IR
(KBr, cm-1): 2119 (m, νAuCtC). H NMR (CDCl3, δ): 4.21 (s, 5
1
H, C5H5), 4.38 (dpt, JHP ) 2.8 Hz, JHH ) 1.8 Hz, 2 H, HR/C5H4),
4.56 (dpt, JHP ) 1.0 Hz, JHH ) 1.8 Hz, 2 H, Hꢀ/C5H4), 7.34–7.38
(m, 2 H, C5H4N), 7.40–7.65 (m, 10 H, C6H5), 8.47–8.51 (m, 2 H,
(25) (a) Grosshenny, V.; Romero, F. M.; Ziessel, R. J. Org. Chem. 1997,
62, 1491. (b) Schwab, P. F. H.; Fleischer, F.; Michl, J. J. Org. Chem. 2002,
67, 443. (c) Polin, J.; Schmohel, E.; Balzani, V. Synthsis 1998, 3, 321.
(26) McIlroy, S. P.; Clo, E.; Nikolajsen, L.; Frederiksen, P. K.; Nielsen,
C. B.; Mikkelsen, K. V.; Gothelf, K. V.; Ogilby, P. R. J. Org. Chem. 2005,
70, 1134.
C5H4N). 13C{1H} NMR (CDCl3, δ): 69.6 (d, JCP ) 67.2 Hz, Ci/
1
C5H4), 70.2 (C5H5), 72.5 (d, JCP ) 8.6 Hz, Cꢀ/C5H4), 73.7 (d,
3
2JCP ) 13.9 Hz, CR/C5H4), 101.5 (CtC), 126.7 (CH/C5H4N), 129.0
(d, 3JCP ) 11.5 Hz, Cm/C6H5), 131.4 (d, 4JCP ) 2.4 Hz, Cp/C6H5),
(27) (a) Janka, M.; Anderson, G. K.; Rath, N. Organometallics 2004,
23, 4382. (b) Yu, L.; Lindsey, J. S. J. Org. Chem. 2001, 66, 7402. (c)
Holmes, B. T.; Pennington, W. T.; Hanks, T. W. Synth. Commun. 2003,
33, 2447.
132.0 (d, JCP ) 57.1 Hz, Ci/C6H5), 133.4 (Ci/C5H4N), 133.8 (d,
1
2JCP ) 13.4 Hz, Co/C6H5), 149.8 (CH/C5H4N). 31P{1H} NMR
(CDCl3, 101.249 MHz, δ): 36.0 (s, PPh2). (The second signal for
the CtC entity could not be detected.)
(28) Steenwinkel, P.; James, S. L.; Grove, D. M.; Veldman, N.; Spek,
A. L.; van Koten, G. Chem.-Eur. J. 1996, 2, 1440.
(29) Back, S.; Martin, A.; Spek, A. L.; Rheinwald, G.; Lang, H.; van
Koten, G. Organometallics 2001, 20, 1024.
Synthesis of FcPPh2AuCtC-NCNH (3d). To a cooled solution
(-50 °C) of 100 mg (0.46 mmol) HCtC-NCNH (2d) in 50 mL of
diethyl ether was dropwise added 0.27 mL (0.43 mmol) of methyl
lithium (1.6 M in diethyl ether). Stirring was continued for 30 min
at this temperature followed by addition of 150 mg (0.25 mmol)
of FcPPh2AuCl (1). The reaction mixture was allowed to warm to
25 °C. After 15 h of stirring it was filtered through a pad of Celite
and concentrated to 2 mL. The title compound was precipitated by
(30) Price, D. W., Jr.; Dirk, S. M.; Maya, F.; Tour, J. M. Tetrahedron
2003, 59, 2497.
(31) Polin, J.; Schottenberger, H. Org. Synth. 1996, 13, 262.
(32) (a) Rausch, M. D.; Fischer, E. O.; Grubert, H. J. Am. Chem. Soc.
1960, 82, 76. (b) Rausch, M. D.; Siegel, A. J. Org. Chem. 1969, 34, 1974.
(33) James, S. L.; Verspui, G.; Spek, A. L.; van Koten, G. Chem.
Commun. 1996, 1309.
(34) Werner, H.; Prinz, R. Chem. Ber. 1967, 100 (1), 265.
(35) Lang, H.; Herres, M.; Zsolnai, L. Organometallics 1993, 12, 5008.

1224 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
addition of 30 mL of n-pentane. The obtained solid was washed
twice with 10 mL portions of n-pentane and dried in an oil-pump
vacuum to give 3d as a yellow solid. Yield: 110 mg (0.14 mmol,
56% based on 1).
(CDCl3, 101.249 MHz, δ): 36.1 (s, PPh2). (The signals for the CtC
entity could not be detected.)
Synthesis of FcPPh2AuCtCFc (5b). To 50 mL of diethyl amine
containing 185 mg (0.38 mmol) of FcPPh2AuCl (1) and 90 mg
(0.43 mmol) of ethynylferrocene (4b) was added 1 mg of [CuI].
After a reaction period of 2 h at 25 °C the mixture was filtered
through a pad of Celite and all volatile materials were removed in
an oil-pump vacuum. The remaining solid was chromatographed
on silica gel using diethyl ether/n-hexane (4:1, v/v) as eluent. After
removal of the solvents under reduced pressure the product was
obtained as an orange solid. Yield: 225 mg (0.29 mmol, 76% based
on 1).
Anal. Calc for C36H38N2PAuFe (782.5): C, 55.26; H, 4.89; N,
3.58. Found: C, 55.27; H, 4.95; N, 3.14. Mp: 75 °C. IR (KBr,
cm-1): 2103 (m, νAuC≡C). 1H NMR (CDCl3, δ): 2.21 (s, 12 H,
NCH3), 3.36 (s, 4 H, NCH2), 4.20 (s, 5 H, C5H5), 4.38 (dpt, JHP
)
2.8 Hz, JHH ) 1.9 Hz, 2 H, HR/C5H4), 4.54 (dpt, JHP ) 1.0 Hz, JHH
) 1.9 Hz, 2 H, Hꢀ/C5H4), 7.17 (s, 1 H, C6H3), 7.34–7.50 (m, 8 H,
C6H5 + C6H3), 7.55–7.65 (m, 4 H, C6H5). 13C{1H} NMR (CDCl3,
1
δ): 45.4 (NCH3), 64.1 (NCH2), 69.8 (d, JCP ) 65.7 Hz, Ci/C5H4)
3
2
70.1 (C5H5), 72.4 (d, JCP ) 8.6 Hz, Cꢀ/C5H4), 73.6 (d, JCP
)
Anal. Calc for C34H28AuFe2P (776.03): C, 52.58; H, 3.64. Found:
C, 52.33; H, 3.88. Mp: >82 °C (dec). IR (KBr, cm-1): 2112 (m,
13.4 Hz, CR/C5H4), 104.2 (CtC), 124.5 (Ci/C6H3), 128.6 (CH/
C6H3), 128.8 (d, 3JCP ) 11 Hz, Cm/C6H5), 131.2 (d, 4JCP ) 1.9 Hz,
1
ν
AuCtC). H NMR (CDCl3, δ): 4.13 (pt, JHH ) 1.8 Hz, 2 H, Hꢀ/
Cp/C6H5), 132.1 (CH/C6H3), 132.2 (d, JCP ) 56.2 Hz, Ci/C6H5),
1
C5H4/FcCtC), 4.19 (s, 5 H, C5H5/FcPPh2), 4.24 (s, 5 H, C5H5/
FcCtC), 4.38 (dpt, JHP ) 3.0 Hz, JHH ) 1.8 Hz, 2 H, HR/C5H4/
FcPPh2), 4.47 (pt, JHH ) 1.8 Hz, 2 H, HR/C5H4/FcCtC), 4.54 (dpt,
JHP ) 1.0 Hz, JHH ) 1.8 Hz, 2 H, Hꢀ/C5H4/FcPPh2), 7.37–7.66
(m, 10 H, C6H5). 13C{1H} NMR (CDCl3, δ): 67.8 (Ci/C5H4/
133.8 (d, 2JCP ) 13.8 Hz, Co/C6H5), 138.7 (Ci/C6H3). 31P{1H} NMR
(CDCl3, 101.249 MHz, δ): 36.4 (s, PPh2). (The second signal for
the CtC entity could not be detected.)
Synthesis of FcPPh2AuCtC-NCNI (3e). To a solution of 150
mg (0.44 mmol) of HCtC-NCNI (2e) in 25 mL of diethyl ether
was added LiN(SiMe3)2 (70 mg, 0.42 mmol) in a single portion,
and the reaction mixture was stirred for 3 h at ambient temperature.
After addition of 150 mg (0.25 mmol) of FcPPh2AuCl (1) stirring
was continued for 15 h. The reaction mixture was then filtered
through a pad of Celite and concentrated to 2 mL. Addition of 30
mL of n-pentane led to the precipitation of 3e. The yellow
precipitate was washed twice with 10 mL portions of n-pentane
and dried in an oil-pump vacuum. Yield: 140 mg (0.15 mmol, 62%
based on 1).
1
FcCtC), 67.9 (CH/C5H4/FcCtC), 70.0 (d, JCP ) 66.3 Hz, Ci/
C5H4/FcPPh2), 70.1 (C5H5/FcPPh2), 70.1 (C5H5/FcCtC), 72.0 (CH/
C5H4/FcCtC), 72.4 (d, 3JCP ) 8.5 Hz, Cꢀ/C5H4/FcPPh2), 73.7 (d,
3
2JCP ) 13.8 Hz, CR/C5H4/FcPPh2), 128.9 (d, JCP ) 11.1 Hz, Cm/
4
1
C6H5), 131.2 (d, JCP ) 2.3 Hz, Cp/C6H5), 132.4 (d, JCP ) 57.1
Hz, Ci/C6H5), 133.9 (d, 2JCP ) 13.8 Hz, Co/C6H5). 31P{1H} NMR
(CDCl3, 101.249 MHz, δ): 36.4 (s, PPh2). (The signals for the CtC
entity could not be detected.)
Synthesis of FcPPh2AuCtCRc (5c). Compound 5c was
prepared in the same manner as 5b. To 185 mg (0.38 mmol) of
FcPPh2AuCl (1) and 110 mg (0.43 mmol) of ethynylruthenocene
(4c) dissolved in 50 mL of diethyl amine was added 1 mg of [CuI].
After appropriate workup, 5c was obtained as an orange solid. Yield:
192 mg (0.23 mmol, 61% based on 1).
Anal. Calc for C36H37N2PIAuFe (908.4): C, 47.60; H, 4.11; N,
3.08. Found: C, 48.53; H, 4.31; N, 3.04. Mp: >150 °C (dec). IR
1
(KBr, cm-1): 2117 (m, νAuCtC). H NMR (CDCl3, δ): 2.29 (s, 12
H, NCH3), 3.44 (s, 4 H, NCH2), 4.20 (s, 5 H, C5H5), 4.38 (dpt, JHP
) 2.8 Hz, JHH ) 1.9 Hz, 2 H, HR/C5H4), 4.55 (dpt, JHP ) 1.0 Hz,
JHH ) 1.9 Hz, 2 H, Hꢀ/C5H4), 7.36–7.50 (m, 8 H, C6H5 + C6H2),
7.55–7.66 (m, 4 H, C6H5). 13C{1H} NMR (CDCl3, δ): 45.6 (NCH3),
68.2 (d, 1JCP ) 66.8 Hz, Ci/C5H4), 69.0 (NCH2), 70.1 (C5H5), 72.4
Anal. Calc for C34H28AuFePRu (822.00): C, 49.64; H, 3.43.
Found: C, 49.78; H, 3.69. Mp: >90 °C (dec). IR (KBr, cm-1):
1
2107 (m, νAuCtC). H NMR (CDCl3, δ): 4.17 (s, 5 H, C5H5/Fc),
4.38 (dpt, JHP ) 3.0 Hz, JHH ) 1.8 Hz, 2 H, HR/C5H4/Fc), 4.49
(pt, JHH ) 1.7 Hz, 2 H, Hꢀ/C5H4/Rc), 4.53 (dpt, JHP ) 1.0 Hz, JHH
) 1.8 Hz, 2 H, Hꢀ/C5H4/Fc) 4.47 (pt, JHH ) 1.8 Hz, 2 H, HR/
C5H4/Rc), 4.61 (s, 5 H, C5H5/Rc), 7.35–7.63 (m, 10 H, C6H5).
13C{1H} NMR (CDCl3, δ): 69.9 (CH/C5H4/Rc), 70.1 (C5H5/Fc),
70.6 (d, 1JCP ) 41.6 Hz, Ci/C5H4/Fc), 71.9 (C5H5/Rc), 72.4 (d, 3JCP
3
2
(d, JCP ) 8.5 Hz, Cꢀ/C5H4), 73.6 (d, JCP ) 13.8 Hz, CR/C5H4),
103.4 (d, JCP ) 27 Hz, CtC), 106.0 (C-I/C6H2), 124.3 (Ci/C6H2),
128.8 (d, 3JCP ) 11.3 Hz, Cm/C6H5), 131.3 (d, 4JCP ) 2.2 Hz, Cp/
C6H5), 132.1 (d, 1JCP ) 57.2 Hz, Ci/C6H5), 133.0 (CH/C6H2), 133.8
2
(d, JCP ) 13.8 Hz, Co/C6H5), 141.7 (Ci/C6H2), 171.1 (CtC).
2
) 8.4 Hz, Cꢀ/C5H4/Fc), 73.7 (d, JCP ) 13.8 Hz, CR/C5H4/Fc),
31P{1H} NMR (CDCl3, 101.249 MHz, δ): 36.5 (s, PPh2).
3
74.5 (CH/C5H4/Rc), 128.8 (d, JCP ) 11.1 Hz, Cm/C6H5), 131.2
4
1
(d, JCP ) 2.3 Hz, Cp/C6H5), 132.4 (d, JCP ) 57.1 Hz, Ci/C6H5),
Synthesis of FcPPh2Au[(CtCC6H5)Cr(CO)3] (5a). To 150 mg
(0.25 mmol) of FcPPh2AuCl (1) dissolved in 50 mL of degassed
diethyl amine was added 80 mg (0.33 mmol) of (η6-
C6H5CtCH)Cr(CO)3 (4a) and 1 mg of [CuI]. The resulting mixture
was stirred for 5 h at 25 °C. Afterward all volatiles were removed
under reduced pressure and the remaining residue was purified by
column chromatography on silica gel using a mixture of dichlo-
romethane/n-hexane (1:1, v/v) as eluent. After removal of the
solvents in an oil-pump vacuum complex 5a could be isolated as
an orange solid. Yield: 145 mg (0.18 mmol, 72% based on 1).
133.9 (d, JCP ) 13.8 Hz, Co/C6H5). 31P{1H} NMR (CDCl3,
2
101.249 MHz, δ): 36.3 (s, PPh2). (The signals for the CtC entity
and the Ci/Rc could not be detected.)
Synthesis of FcPPh2AuCtC-C6H4-4-CtN-[Ru] (7). To 30 mg
(0.04 mmol) of [Ru]NtN[Ru] (6) in 15 mL of dichloromethane
was added 60 mg (0.09 mmol) of FcPPh2AuCtC-C6H4-4-CtN
(3b) in a single portion. The reaction solution was stirred for 3 h
at 25 °C, whereby the color of the solution changed from orange
to deep red. The solvent was concentrated to 3 mL, and the product
was precipitated by addition of 20 mL of n-hexane, washed twice
with 10 mL portions of diethyl ether, and dried in an oil-pump
vacuum. Complex 7 was obtained as a red solid. Yield: 75 mg
(0.07 mmol, 88% based on 6).
Anal. Calc for C33H24O3PAuCrFe (804.3): C, 49.28; H, 3.01.
Found: C, 49.13; H, 3.15. Mp: >87 °C (dec). IR (KBr, cm-1):
2122 (m, νAuCtC), 1963, 1883 (s, νCO). 1H NMR (CDCl3, δ): 4.21
(s, 5 H, C5H5), 4.37 (br s, HR/C5H4), 4.55 (br s, Hꢀ/C5H4), 5.16
(pt, JHH ) 6.3 Hz, 1 H, C6H5/Cr), 5.32 (pt, JHH ) 6.3 Hz, 2 H,
C42H42N4Cl2PAuFeRu (1058.59): C, 47.65; H, 4.00; N, 5.29;
3
4
C6H5/Cr), 5.53 (dd, JHH ) 6.5 Hz, JHH ) 1 Hz, 2 H, C6H5/Cr),
Found: C, 47.32; H, 3.73; N, 5.47. Mp: >105 °C (dec). IR (KBr,
7.38–7.64 (m, 10 H, C6H5). 13C{1H} NMR (CDCl3, δ): 69.6 (d,
1
cm-1): 2199 (m, νCtN), 2112 (w, νAuCtC). H NMR (CDCl3, δ):
1JCP ) 65.2 Hz, Ci/C5H4), 70.2 (C5H5), 72.5 (d, JCP ) 8.5 Hz,
3
2.65 (s, 12 H, NCH3), 4.10 (s, 4 H, NCH2), 4.22 (s, 5 H, C5H5),
4.38 (br s, 2 H, HR/C5H4), 4.56 (br s, 2 H, Hꢀ/C5H4), 7.20 (d, 3JHH
) 7.8 Hz, 2 H, C5H3N), 7.39–7.74 (m, 15 H, C6H5 + C6H4 +
C5H3N). 31P{1H} NMR (CDCl3, 101.249 MHz, δ): 36.5 (s, PPh2).
MS (ESI-TOF, m/z): 1058.2 (40) [M]+, 365.0 (30) [M - 3b]+.
Cꢀ/C5H4), 73.7 (d, 2JCP ) 13.7 Hz, CR/C5H4), 90.0 (CH/C6H5), 92.4
(CH/C6H5), 95.0 (Ci/C6H5), 95.9 (CH/C6H5), 129.0 (d, 3JCP ) 11.3
Hz, Cm/C6H5), 131.4 (Cp/C6H5), 132.0 (d, 1JCP ) 52.5 Hz, Ci/C6H5),
133.8 (d, JCP ) 13.7 Hz, Co/C6H5), 223.1 (CO). 31P{1H} NMR
2

Diphenylphosphinoferrocene Gold(I) Acetylides
Organometallics, Vol. 27, No. 6, 2008 1225
Synthesis of [FcPPh2AuCtC-C5H4N-Cu{(Me3SiCtC)2[Ti]}]-
OTf (9). To 50 mg (0.075 mmol) of FcPPh2AuCtC-C5H4N (3c)
dissolved in diethyl ether (40 mL) was added 60 mg (0.08 mmol)
of {[Ti](µ-σ,π-CtCSiMe3)2]}CuOTf (8a), and the resulting reaction
mixture was stirred for 2 h. Afterward the resulting precipitate was
filtered, washed with diethyl ether (10 mL), and dried in an oil-
pump vacuum. Complex 9 was obtained as a golden-yellow solid.
Yield: 75 mg (0.054 mmol, 71% based on 3c).
in vacuum yielded 13a as an orange solid. Yield: 75 mg (0.065
mmol, 48% based on 11a).
C48H44N4PAuFePt (1155.77). IR (KBr, cm-1): 2103 (m, νAuCtC),
2080 (m, νPtCtC). Further characterization was not possible, due to
the high insolubility of 13a in organic solvents (vide supra).
Synthesis of FcPPh2AuCtC-NCN-Pt-CtC-C6H4-4-CtN
(13b). Experimental conditions and workup were identical to those
for compound 13a. Experimental details: 12b (70 mg, 0.13 mmol),
FcPPh2AuCl (1) (100 mg, 0.166 mmol). Yield: 60 mg (0.054 mmol,
42% based on 12b).
Anal. Calc for C56H67O3NF3PSSi4AuCuFeTi (1398.8): C, 48.09;
H, 4.83; N, 1.00. Found: C, 48.11; H, 4.76; N, 1.01. Mp: >124 °C
1
(dec). IR (KBr, cm-1): 2126 (m, νAuCtC), 1915 (m, νTiCtC). H
C45H41N3PAuFePt (1102.7). IR (KBr, cm-1): 2223 (m, νCtN),
2096 (m, νAuCtC), 2079 (m, νPtCtC). MS (ESI-TOF, m/z): 1103.2
[M + H]+. Further characterization was not possible, due to the
high insolubility of 13b in organic solvents (vide supra).
Synthesis of FcPPh2AuCtC-bipy[Mo(CO)4] (15). To 70 mg
(0.094 mmol) of FcPPh2AuCtC-bipy (3a) dissolved in 30 mL of
dichloromethane/tetrahydofuran (ratio 5:1) was added 30 mg (0.1
mmol) of (nbd)Mo(CO)4 (14). After a few minutes the color of the
solution turned from yellow to dark red. Stirring was continued
for 15 h at 25 °C. Afterward all volatiles were removed in an oil-
pump vacuum and the residue was washed twice with 15 mL
portions of diethyl ether and dried in an oil-pump vacuum.
Compound 15 was obtained as a dark red solid (Yield: 70 mg, 0.073
mmol, 78% based on 3a).
NMR (CDCl3, δ): -0.06 (s, 18 H, SiMe3), 0.26 (s, 18 H, SiMe3),
4.22 (s, 5 H, C5H5), 4.38 (dpt, JHP ) 2.7 Hz, JHH ) 1.9 Hz, 2 H,
HR/C5H4), 4.58 (dpt, JHP ) 1.0 Hz, JHH ) 1.9 Hz, 2 H, Hꢀ/C5H4),
6.26–6.32 (m, 8 H, C5H4SiMe3), 7.41–7.65 (m, 12 H, C6H5 +
C5H4N), 8.53–8.57 (m, 2 H, C5H4N). 31P{1H} NMR (CDCl3,
101.249 MHz, δ): 36.1 (s, PPh2). MS (ESI-TOF, m/z): 1248.2 (100)
[M - CF3SO3]+, 579.2 (10) [M - 3c]+.
Synthesis of Me3SiCtC-NCN-Pt-CtC-bipy (11a). A 140 mg
(0.78 mmol) amount of 5-ethynyl-2,2′-bipyridyl (2a) was dissolved
in 100 mL of diethyl ether, and at -80 °C 0.45 mL (0.72 mmol)
of nBuLi (1.6 M in n-hexane) was slowly added. The resulting violet
solution was stirred for 30 min at this temperature, and then 10
(250 mg, 0.48 mmol) was added in a single portion. The mixture
was allowed to warm to 25 °C, and stirring was continued for 16 h.
All volatiles were evaporated in vacuum, and the residue was
dissolved in dichloromethane (20 mL) and filtered through a pad
of Celite. The solution was concentrated to 3 mL, and addition of
n-hexane (50 mL) led to the precipitation of 11a. The separation
of the solid material was effected by centrifugation. After washing
it twice with diethyl ether (10 mL), complex 11a was obtained as
an off-white solid. Yield: 240 mg (0.36 mmol, 75% based on 10).
Anal. Calc for C38H26O4AuFeMoN2P (954.37): C, 47.82; H, 2.75;
N, 2.94. Found: C, 47.67; H, 2.76, N, 3.02. Mp: >175 °C (dec).
IR (KBr, cm-1): 2119 (m, νAuCtC), 2011, 1890, 1867, 1829 (s,
ν
CO). 1H NMR (CDCl3, δ): 4.23 (s, 5 H, C5H5), 4.41 (bs, 2 H,
3
HR/C5H4), 4.58 (bs, 2 H, Hꢀ/C5H4), 7.33 (ddd, JH5′H4′ ) 7.6 Hz,
3JH5′H6′ ) 5 Hz, 4JH5′H3′ ) 1 Hz, 1 H, H5′/bipy), 7.42–7.66 (m, 10
3
3
4
H, C6H5), 7.89 (ddd, JH4′H3′ ) JH4′H5′ ) 8 Hz, JH4′H6′ ) 1.4 Hz,
1 H, H4′/bipy), 7.91–8.05 (m, 3 H, H3,H3′,H4/bipy), 9.12 (d, 3JH6′H5′
C29H34N4SiPt (661.78). IR (KBr, cm-1): 2146 (m, νSiCtC), 2089
) 5 Hz, 1 H, H6′/bipy), 9.27 (d, JH6H4 ) 1.2 Hz, 1 H, H6/bipy).
4
1
(m, νPtCtC). H NMR (CDCl3, δ): 0.22 (s, 9 H, SiMe3), 3.22 (s,
31P{1H} NMR (CDCl3, 101.249 MHz, δ): 36.19 (s, PPh2).
3
3JHPt ) 42.8 Hz, 12 H, NCH3), 4.09 (s, JHPt ) 43.6 Hz, 4 H,
Synthesis of [FcPPh2AuCtC-bipy-Cu{(Me3SiCtC)2[Ti]}]PF6
(16a). To 65 mg (0.087 mmol) of FcPPh2AuCtC-bipy (3a)
dissolved in 30 mL of tetrahydrofuran were added 65 mg (0.085
mmol) of [{[Ti](µ-σ,π-CtCSiMe3)2}Cu(NtCCH3)]PF6 (8b). The
reaction solution was stirred for 3 h at 25 °C. Afterward it was
filtered through a pad of Celite and all volatiles were removed under
reduced pressure. The residue was washed twice with 15 mL
portions of petroleum ether and dried in an oil-pump vacuum.
Complex 16a was obtained as an orange-red solid. Yield: 120 mg
(0.082 mmol, 96% based on 8b).
3
3
NCH2), 7.04 (s, 2 H, C6H2), 7.24 (ddd, JH5′H4′ ) 8 Hz, JH5′H6′
)
4.8 Hz, 4JH5′H3′ ) 1 Hz, 1 H, H5′/bipy), 7.73–7.81 (m, 2 H, H4,H4′/
bipy), 8.23 (dd, 3JH3H4 ) 8.3 Hz, 5JH3H6 ) 0.6 Hz, 1 H, H3/bipy),
3
4
5
8.35 (ddd, JH3H4′ ) 8 Hz, JH3′H5′ ) 1 Hz, JH3′H6′ ) 1 Hz, 1 H,
3
4
5
H3′/bipy), 8.65 (ddd, JH6′H5′ ) 4.8 Hz, JH6′H4′ ) 1.8 Hz, JH6′H3′
4
5
) 1 Hz, 1 H, H6′/bipy), 8.69 (dd, JH6H4 ) 2.4 Hz, JH6H3 ) 0.6
Hz, 1 H, H6/bipy).
Synthesis of HCtC-NCN-Pt-CtC-bipy (12a). To 11a (200
mg, 0.30 mmol) dissolved in dichloromethane (50 mL) was added
0.35 mL (0.35 mmol) of [nBu4N]F (1 M in tetrahydrofuran). After
stirring for 2 h at 25 °C all volatiles were evaporated under reduced
pressure and the residue was extracted with ethanol (3 × 10 mL).
Separation by centrifugation and drying in an oil-pump vacuum
yielded 12a as a pale brown solid. Yield: 90 mg (0.15 mmol, 51%
based on 11a).
Anal. Calc for C60H70AuCuF6FeN2P2Si4Ti (1471.76): C, 48.97;
H, 4.79; N, 1.90. Found: C, 48.70; H, 4.68; N, 2.18. Mp: >172 °C
(dec). IR (KBr, cm-1): 2118 (m, νAuCtC), 1924 (w, νTiCtC), 841
1
(s, νPF). H NMR (CDCl3, δ): -0.49 (s, 18 H, SiMe3), 0.27 (s, 9
H, SiMe3), 0.28 (s, 9 H, SiMe3), 4.21 (s, 5 H, C5H5), 4.39 (dpt, JHP
) 2.5 Hz, JHH ) 1.9 Hz, 2 H, HR/C5H4/Fc), 4.58 (br s, 2 H, Hꢀ/
C5H4/Fc), 6.26–6.30 (m, 8 H, C5H4SiMe3), 7.41–7.64 (m, 10 H,
C6H5) 7.69 (dd, 3JH5′H4′ ) 7.8 Hz, 3JH5′H6′ ) 5 Hz, 1 H, H5′/bipy),
C26H26N4Pt (589.6). IR (KBr, cm-1): 3287 (m, νtC-H), 2080 (s,
ν
PtC≡C). 1H NMR (CDCl3, δ): 3.01 (s, 1 H, tCH), 3.23 (s, 3JHPt
)
42.8 Hz, 12 H, NCH3), 4.11 (s, 3JHPt ) 43.6 Hz, 4 H, NCH2), 7.05
(s, 2 H, C6H2), 7.24 (ddd, 3JH5′H4′ ) 8 Hz, 3JH5′H6′ ) 4.8 Hz, 4JH5′H3′
) 1 Hz, 1 H, H5′/bipy), 7.73–7.81 (m, 2 H, H4,H4′/bipy), 8.23
3
4
8.18 (dd, JH4H3 ) 8.5 Hz, JH4H6 ) 2 Hz, 1 H, H4/bipy), 8.22
4
(ddd,
3JH4′H3′
)
3JH4′H5′ ) 7.8 Hz, JH4′H6′ ) 1.8 Hz, 1 H, H4′/
bipy), 8.39 (d, 3JH3′H4′ ) 7.8 Hz, 1 H, H3′/bipy), 8.50 (d, 3JH3H4
)
3
5
3
(dd, JH3H4 ) 8.3 Hz, JH3H6 ) 0.6 Hz, 1 H, H3/bipy), 8.35 (ddd,
8.5 Hz, 1 H, H3/bipy), 8.53 (d, JH6′H5′ ) 4.4 Hz, 1 H, H6′/bipy),
3JH3H4′ ) 8 Hz, JH3′H5′ ) 1 Hz, JH3′H6′ ) 1 Hz, 1 H, H3′/bipy),
8.65 (ddd, JH6′H5′ ) 4.8 Hz, JH6′H4′ ) 1.8 Hz, JH6′H3′ ) 1 Hz, 1
H, H6′/bipy), 8.69 (dd, JH6H4 ) 2.4 Hz, JH6H3 ) 0.6 Hz, 1 H,
H6/bipy).
8.56 (d, 4JH6H4 ) 2 Hz, 1 H, H6/bipy). 13C{1H} NMR (CDCl3, δ):
4
5
3
4
5
1
-0.6 (SiMe3), 0.17 (SiMe3), 0.23 (SiMe3), 69.2 (d, JCP ) 68.2
4
5
Hz, Ci/C5H4/Fc), 70.1 (C5H5/Fc), 72.7 (d, 3JCP ) 8.6 Hz, Cꢀ/C5H4/
Fc), 73.7 (d, JCP ) 13.8 Hz, CR/C5H4/Fc), 98.7 (AuCtC), 115.2
2
Synthesis of FcPPh2AuCtC-NCN-Pt-CtC-bipy (13a). Com-
pound 12a (80 mg, 0.136 mmol) and FcPPh2AuCl (1) (100 mg,
0.166 mmol) were dissolved in 15 mL of tetrahydrofuran and 10
mL of diethyl amine. After addition of 1 mg of [CuI] the resulting
reaction mixture was stirred overnight at 25 °C. The solvents were
evaporated under reduced pressure, and the residue was extracted
with acetone (3 × 10 mL). Separation by centrifugation and drying
(CH/C5H4), 115.3 (CH/C5H4), 117.2 (CH/C5H4), 117.3 (CH/C5H4),
122.0 (bipy), 122.9 (bipy), 122.9 (Ci/C5H4), 123.3 (Ci/C5H4), 125.8
(bipy), 126.8 (bipy), 129.1 (d, JCP ) 11.3 Hz, Cm/C6H5), 131.6
3
(d, JCP ) 2.4 Hz, Cp/C6H5), 131.7 (d, JCP ) 58.3 Hz, Ci/C6H5),
133.7 (TiCtC), 133.8 (d, 2JCP ) 13.7 Hz, Co/C6H5), 140.5 (bipy),
142.7 (bipy), 147.8 (bipy), 149.2 (bipy), 150.7 (bipy), 151.8 (bipy),
165.9 (TiCtC). 31P{1H} NMR (CDCl3, 101.249 MHz, δ): 36.2
4
1

1226 Organometallics, Vol. 27, No. 6, 2008
Packheiser et al.
1
(s, PPh2), -145.1 (septuplett, JPF ) 713 Hz, PF6). (The second
radiation (λ ) 0.71073 Å) at 293(2) K (3b, 3e, 5b, 5c), 203(2) K
(3a), and 183(2) (16a) using oil-coated shock-cooled crystals.36
The structures were solved by direct methods using SHELXS-9737
and refined by full-matrix least-squares procedures on F2 using
SHELXL-97.38 All non-hydrogen atoms were refined anisotropi-
cally, and a riding model was employed in the refinement of the
hydrogen atom positions. In 3e the NMe2 group is disordered and
has been refined to split occupancies of 0.35/0.65 (N1, C32, and
C33).
signal for the AuCtC entity could not be detected.)
Synthesis of [FcPPh2AuCtC-bipy-Ag{(Me3SiCtC)2[Ti]}]-
ClO4 (16b). Experimental conditions and workup were the same
as for the preparation of 16a. Specific experimental details: {[Ti](µ-
σ,π-CtCSiMe3)2]}AgOClO3(8c)(75mg,0.105mmol),FcPPh2AuCtC-
bipy (3a) (80 mg, 0.107 mmol), 2 h stirring, orange solid. Yield:
115 mg (0.078 mmol), 74% based on 8c.
Anal. Calc for C60H70O4AgAuClFeN2PSi4Ti (1470.56): C, 49.01;
H, 4.80; N, 1.91. Found: C, 49.00; H, 4.80; N, 1.88. Mp: >145 °C
(dec). IR (KBr, cm-1): 2116 (m, νAuCtC), 1952 (w, νTiCtC), 1097
(s, νClO). 1H NMR (CDCl3, δ): -0.30 (br s, 18 H, SiMe3), 0.27 (s,
18 H, SiMe3), 4.20 (s, 5 H, C5H5/Fc), 4.38 (br s, 2 H, HR/C5H4/
Fc), 4.58 (br s, 2 H, Hꢀ/C5H4/Fc), 6.42 (pt, JHH ) 2.2 Hz, 4 H,
C5H4SiMe3), 6.49 (pt, JHH ) 2.2 Hz, 4 H, C5H4SiMe3) 7.39–7.65
Acknowledgment. We are grateful to the Deutsche
Forschungsgemeinschaft and the Fonds der Chemischen
Industrie for generous financial support.
Supporting Information Available: Tables of atomic coordi-
nates, bond lengths, angles, torsion angles, and anisotropic displace-
ment parameters for 3a, 3b, 3e, 5b, 5c, and 16a and a cyclic
voltammogram of 9. This material is available free of charge via
the Internet at http://pubs.acs.org.
3
4
(m, 11 H, C6H5 + H5′/bipy), 8.13 (dd, JH4H3 ) 8.4 Hz, JH4H6
)
2 Hz, 1 H, H4/bipy), 8.18 (ddd, 3JH4′H3′ ) 3JH4′H5′ ) 8 Hz, 4JH4′H6′
) 1.5 Hz, 1 H, H4′/bipy), 8.31 (d, 3JH3H4 ) 8.4 Hz, 1 H, H3/bipy),
3
3
8.41 (d, JH3′H4′ ) 8 Hz, 1 H, H3′/bipy), 8.58 (d, JH6′H5′ ) 5 Hz,
4
5
OM701021Y
1 H, H6′/bipy), 8.64 (dd, JH6H4 ) 2 Hz, JH6H3 ) 0.6 Hz, 1 H,
H6/bipy). 31P{1H} NMR (CDCl3, 101.249 MHz, δ): 36.1 (s, PPh2).
Crystal Structure Determinations. Crystal data for 3a, 3b, 3e,
5b, 5c, and 16a are presented in Tables 3 (3a, 3b, 3e) and 4 (5b,
5c, 16a). The data for 3a, 3e, and 16a were collected on a Bruker
Smart CCD 1k diffractometer and for 3b, 5b, and 5c on a Oxford
Gemini S diffractometer with graphite-monochromatized Mo KR
(36) (a) Kottke, T.; Stalke, D. J. Appl. Crystallogr. 1993, 26, 615. (b)
Kottke, T.; Lagow, R. J.; Stalke, D. J. Appl. Crystallogr. 1996, 29, 465. (c)
Stalke, D. Chem. Soc. ReV. 1998, 27, 171.
(37) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(38) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; University of Göttingen, 1997.