Synthesis, crystal and molecular structure of gold(I) thiophenolate with 4′-ferrocenyl[1,1′]biphenylisocyanides

Article abstract of DOI:10.1016/j.jorganchem.2009.09.043

The syntheses of ferrocenylbiphenylisocyanide gold(I) thiophenolato complexes are described. The preparative route starts from ferrocenylphenylbromide and proceeds in six steps to yield the desired gold(I) complexes, (thiophenolato)gold{(4′-ferrocenyl[1,1′]biphenyl-4-yl)isocya nide} (11) and (thiophenolato)gold{(4′-ferrocenyl-3,5-dimethyl[1,1′]bipheny l-4-yl)isocyanide} (12) in good yields. The synthetic pathways were developed as a first step toward realizing the goal of preparing metallomesogens based on ferrocenyl-polyphenylenes coordinated to gold(I) thiophenolates, in which long chain alkoxy groups are substituted para to sulfur on the phenyl ring. The crystal structures of (chloro)gold{(4^′-ferrocenyl[1,1′]biphenyl-4-yl)is ocyanide} (9) and 12 are reported. Complex 9 crystallizes in the space group P2₁/c and 12 crystallizes in P2₁/n. Complexes 9 and 12 show short intermolecular Au-Au contacts of 3.3765(7) ? and 3.3334(3) ?, respectively.

Full text of DOI:10.1016/j.jorganchem.2009.09.043

Journal of Organometallic Chemistry 695 (2010) 304–309
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Note
Synthesis, crystal and molecular structure of gold(I) thiophenolate with
40-ferrocenyl[1,10]biphenylisocyanides
a
a
b
b
c,
**
V.P. Dyadchenko a, , N.M. Belov , D.A. Lemenovskii , M.Yu. Antipin , K.A. Lyssenko , A.E. Bruce
,
*
M.R.M. Bruce c
a Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory, 1-3, Moscow 119992, Russian Federation
b Institute of Elemento-Organic Compounds (INEOS), Vavilova, 28, Moscow 119991, Russian Federation
c Department of Chemistry, University of Maine, Orono, ME 04469, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
The syntheses of ferrocenylbiphenylisocyanide gold(I) thiophenolato complexes are described. The pre-
parative route starts from ferrocenylphenylbromide and proceeds in six steps to yield the desired gold(I)
complexes, (thiophenolato)gold{(40-ferrocenyl[1,10]biphenyl-4-yl)isocyanide} (11) and (thiophenola-
to)gold{(40-ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-yl)isocyanide} (12) in good yields. The synthetic
pathways were developed as a first step toward realizing the goal of preparing metallomesogens based
on ferrocenyl-polyphenylenes coordinated to gold(I) thiophenolates, in which long chain alkoxy groups
are substituted para to sulfur on the phenyl ring. The crystal structures of (chloro)gold{(40 -ferroce-
nyl[1,10]biphenyl-4-yl)isocyanide} (9) and 12 are reported. Complex 9 crystallizes in the space group
P21/c and 12 crystallizes in P21/n. Complexes 9 and 12 show short intermolecular Au–Au contacts of
3.3765(7) Å and 3.3334(3) Å, respectively.
Received 19 July 2009
Received in revised form 16 September
2009
Accepted 26 September 2009
Available online 5 October 2009
Keywords:
Gold(I)
Isocyanides
Thiophenolate
Ferrocenyl
Ó 2009 Elsevier B.V. All rights reserved.
Liquid crystals
Metallomesogen
1. Introduction
ization of the complex can be explained by formation of dimers
due to close intermolecular contacts between the sulfur atom
In our previous papers we reported on the design and synthesis
of new ‘‘calamitic” liquid crystals (LC) based on ferrocenyl-poly-
phenylenes of type I (Scheme 1) [1,2]. The ‘‘bridging” –O–C(@O)–
moiety in molecules of type I can be replaced, in principle, with
certain gold(I) containing fragments. The presence of gold in mol-
ecules of this type may provide an additional factor to assist forma-
tion of supramolecular aggregates due to the well-known
‘‘aurophilicity” of gold [3]. In this regard, isocyanide complexes
of gold thiolates are promising because gold forms stable bonds
with sulfur, and the linear isocyanide ligands will not disturb a cal-
amitic structure of the proposed mesogen of type II, which are
gold-containing analogs of type I molecules (Scheme 2).
Here we report on the development of synthetic pathways for
complexes of type III (Scheme 3) as a first step for synthesis of type
II mesogens. There are only a handful of reports of isocyanide com-
plexes of gold thiolates in the literature [4–7]. We have prepared a
stable complex of gold thiophenolate with 2,6-dimethylphenyliso-
cyanide; this work will be reported separately. In this case, stabil-
and the carbon atom of nearby isocyanide ligands. The presence
of methyl groups in the isocyanide ligand is anticipated to increase
the solubility of the complexes.
2. Results and discussion
2.1. Synthesis
The synthesis of complexes of type III begins with preparation
of the corresponding ferrocenyl substituted polyphenylene isocya-
nides. The Suzuki reaction was used for the construction of biphe-
nyl fragments of type III molecules, as described previously [8]. A
modified procedure for preparation of tris(4-ferrocenylphe-
nyl)boroxine, 2, is described here (Eq. (1) and Section 2).
ð1Þ
* Corresponding author. Tel.: +7 095 939 5379; fax: +7 095 932 8846.
** Corresponding author. Tel.: +1 207 581 1182; fax: +1 207 581 1191.
E-mail addresses: dyadchenko@org.chem.msu.ru (V.P. Dyadchenko), abruce@
maine.edu (A.E. Bruce).
The cross-coupling reactions of boroxine 2 with 4-iodoanilines
and with 4-iodo(bromo)formanilides were investigated. For iodo
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.09.043

V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 695 (2010) 304–309
305
diphosgene in the presence of base [10]. This method is convenient
in comparison with other known methods and the preparation of
ferrocene containing isocyanides proceeds with good, reproducible
yields (Eq. (4)).
Scheme 1.
ð2Þ
ð3Þ
Scheme 2.
ð4Þ
Isocyanides 7 and 8 form stable complexes with gold(I) chloride
and with gold(I) thiophenolate. Chloro-complexes 9 and 10 can be
prepared starting from (tetrahydrothiophene)gold chloride (Eq.
(5)). Polymeric gold(I) thiophenolate (1) interacts with isocyanides
7 and 8 in THF solution producing stable complexes 11 and 12 (Eq.
(6)). As we anticipated, the methyl-substituted complex 12 is more
soluble in organic solvents in comparison with complex 11, which
does not contain alkyl groups on the aromatic moiety. Isocyanides
7 and 8 do not form any stable complexes with gold(I) decylthio-
late, i.e. (C10H21SAu)x under the same conditions.
Scheme 3.
derivatives, the yield of the cross-coupling product is significantly
higher in the case of the corresponding formanilide (Table 1). The
yields of cross-coupling products are also higher for the Pd(0) com-
plex, which is typical for this type of reaction.
Ferrocenyl-biphenylamine, 3, was also prepared by reduction of
the corresponding nitro-derivative (Eq. (2)). Formylation of aryl
amines was carried out by the action of acetic formic anhydride
by a modified procedure (Eq. (3)) [9]. The next step in preparing
the target ferrocenylbiphenyl ligands was dehydration of the
substituted formanilides, which was carried out by the action of
Table 1
Synthesis of ferrocenylbiphenylamines by Suzuki reaction.
ð5Þ
ð6Þ
X
R2
R3
Ferrocenyl-
biphenyl
Yield of ferrocenylbiphenyl (%)
[Pd] = (Ph3P)2PdCl2 [Pd] = (Ph3P)4Pd
I
Br
I
H
H
H
C(O)H
H
3
4
5
6
–
–
55
76
68
70
65
85
2.2. Molecular structures of gold(I) complexes
Me
Me C(O)H
The crystal and molecular structure of complex 12 was estab-
I
lished by X-ray and 1H NMR spectroscopy. The X-ray structure

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V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 695 (2010) 304–309
Table 2
ophilic” interactions [3]. The shortest contacts are found in gold
complexes with tertiary phosphines (2.50–3.24 Å). [12] In the thio-
phenolate complex (12), in addition to aurophilic interactions be-
tween dimers, there are shortened contacts between the sulfur
atom of the thiophenolate ligand and the carbon atom of the isocy-
anide ligand (3.467(5) Å). This additional contact, which can be
attributed to charge transfer from the sulfur electron lone pair to
the p* bond of the CN group, leads to a slight deviation in the ex-
pected linear Au–C–N angle to 173.9°. The attractive character of
the PhSꢀ ꢀ ꢀCN contact can be further confirmed by the value of
the C(6)S(1)C(25) angle that is equal to 131°, which is close to
the expected position of the sulfur electron lone pair. At the same
time, we cannot exclude some contribution for dimer stabilization
due to a Auꢀ ꢀ ꢀS intermolecular contact that is equal to 3.74 Å. In
contrast, in the chloride complex (9), the Au–C–N angle is 179.4°
and there is no evidence for additional shortened interactions.
Complex 12 packs in the crystal to form infinite ladder-like ribbons
(Fig. 3).
The principal bond lengths (Å) and angles (°) in complexes 9 and 12.
Complex
9
12
Auꢀ ꢀ ꢀAu
NCꢀ ꢀ ꢀS
Au–S
Au–C
NCAu
CAuX
3.3765(7)
–
–
1.918(10)
179.3(11)
177.3(3)
3.3334(3)
3.467(5)
2.2734(9)
1.954(4)
173.9(3)
175.0(1)
determination of the corresponding complex of gold(I) chloride, 9,
was carried out for comparison.
The X-ray structure investigations of 9 and 12 reveal sub-van-
der-Waals contacts between gold atoms [11], which leads to the
formation of centrosymmetric dimers for both complexes (Table 2
and Figs. 1 and 2). Short intermolecular Auꢀ ꢀ ꢀAu contacts are char-
acteristics of gold(I) complexes and are usually explained by ‘‘aur-
Fig. 1. Centrosymmetric dimers formed by chloro complex 9 in representation of atoms by thermal ellipsoids (p = 50%).
Fig. 2. Centrosymmetric dimers formed by thiophenolato complex 12 in representation of atoms by thermal ellipsoids (p = 50%). The minor positions of the disordered Cp-
ring and phenyl rings are omitted for clarity.
Fig. 3. Infinite ladder-like ribbons formed by complex 12.

V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 695 (2010) 304–309
307
The ‘‘aurophilic” interactions in 9 and 12 are longer and weaker
in comparison to phosphine complexes of gold. We hypothesize
that the aurophilic interactions in 9 and 12 will be strong enough
to promote formation of mesophases but not so strong as to ex-
clude mobility of the intermolecular aggregates, which is necessary
for mesophase existence. We are proceeding with the next step in
the synthesis of molecules of type II, i.e. substituting long chain
alkoxy groups in the para position of the thiophenylate ligands in
order to design gold-containing liquid crystals based on ferroce-
nyl-polyphenyleneisocyanides.
(5.5 ml, 4.6 g, 20 mmol) was added to the reaction mixture at
ꢂ60 °C. The solution was allowed to gradually warm to ꢂ20 °C
with stirring. The cooling bath was removed and stirring was con-
tinued at 20 °C for 40 min. The reaction mixture was quenched
with water (7 ml), after which a 3% HCl solution (about 38 ml)
was added to acidify the solution. The organic layer was separated,
washed several times with water until the pH was neutral, dried
over Na2SO4 and filtered. The solvent was removed in vacuo. m-Xy-
lene (50 ml) was added to the residual orange oil and then re-
moved on a rotary evaporator at a bath temperature of ca. 90 °C
(see a note after description of the experiment). The solid residue
was extracted with boiling petroleum ether (70/100) (3 ꢃ 15 ml)
to remove phenylferrocene. Tris(4-ferrocenylphenyl)boroxine (2)
was obtained as a brick-red powder in a yield of 3.0 g (71%);
decomp. above 270 °C. cf. [8]: decomp. above 270 °C. The 1H
NMR spectrum is consistent with published data; (chloroform-d,
d): 4.07 (s, 5H); 4.39, 4.77, 7.62 and 8.18 (all m, 2H each).
Note: The reaction usually produces a mixture of 2 and 4-ferro-
cenylphenylboronic acid. This boronic acid, in contrast to anhy-
dride 2, is soluble in petroleum ether. The described procedure is
intended for conversion of the mixture into boroxine 2 by removal
of water by azeotropic distillation with xylene. Benzene or toluene
can be used instead of xylene but in these cases the azeotropic dis-
tillation of water should be repeated several times.
3. Experimental
Acetic formic anhydride [13], 4-iodoaniline [14], and 4-iodo-
2,6-dimethylaniline [15] were prepared according to published
procedures. Diphosgene (chloroformic acid trichloromethylester)
was prepared by photochemical chlorination of chloroformic acid
methylester according to a published procedure [10]. All cross-
coupling reactions were carried out according to established proce-
dures [2] by using molar ratios of boroxine (3):aryliodide(bro-
mide):K2CO3:catalyst ꢁ 1:3:9:0.1. Anhydrous THF and dry
chloroform were used in all experiments.
3.1. 4-Bromoformanilide
3.5. 40-Ferrocenyl [1,10]biphenyl-4-amine (3)
A solution of 4-bromoaniline (2.00 g; 0.011 mol) in THF (15 ml)
was added with stirring to a cold (ꢂ20 °C) solution of acetic formic
anhydride (2.75 g; 0.031 mol) in THF (5 ml). The reaction mixture
was stirred at ꢂ20 °C for 30 min. The solvent was removed in vacuo
and the residue was recrystallized from an ethanol–water mixture
(ca. 2:1). Yield: 1.90 g (86%), m.p. 110–112 °C, cf. [16]: m.p. 117 °C.
A
mixture of 1.60 g (4.2 mmol) of 40-ferrocenyl-4-nitro-
[1,10]biphenyl [17], 15 ml of 30% HCl and tin dichloride, SnCl2ꢀ2H2O
(6.55 g; 29 mmol) was stirred under reflux for 3 h. After cooling to
ambient temperature the reaction mixture was poured into a solu-
tion of NaOH (12.0 g; 0.30 mol) in 160 ml water. The product of the
reduction reaction was extracted from the resulting suspension
with ether (six portions of 20 ml). The combined ether extracts
were washed with water and dried over anhydrous Na2SO4. Ether
was removed in vacuo, the solid residue was dissolved in chloro-
form and this solution was filtered through a 3 cm layer of silica
3.2. 4-Iodo-2,6-dimethylformanilide
A solution of 4-iodo-2,6-dimethylaniline (3.00 g; 0.012 mol) in
15 ml of THF was added with stirring to a cold (ꢂ20 °C) solution
of acetic formic anhydride (2.75 g; 0.031 mol) in THF (5 ml). The
reaction mixture was stirred at ꢂ20 °C for 15 min. A precipitate
of 4-iodo-2,6-dimethylformanilide was separated by suction filtra-
tion and air-dried. Yield: 2.87 g (87%), m.p. 234–236 °C, decomp.
Anal. Calc. for C9H10INO: C, 39.30; H, 3.66; N, 5.10. Found: C,
39.45; H, 3.53; N, 5.18%. 1H NMR (chloroform-d, d): 2.19 (s, 6H);
7.46 (m, 2H); 8.02 (s, 0,5H: NH); 8.04 (s, 0,5H: NH); 8.35 (s, 1H).
gel (60 l). After removal of solvent in vacuo, 3 was obtained
(1.30 g; 90%), m.p. 162–165 °C (after recrystallization from tolu-
ene-petroleum ether 1:10 mixture). Anal. Calc. for C22H19FeN: C,
74.80; H, 5.42; N, 3.97. Found: C, 74.70; H, 5.59; N, 3.95%. 1H
NMR (chloroform-d, d): 3.71 (s, 2H); 4.07 (s, 5H); 4.32 (m, 2H);
4.66 (m, 2H); 6.76 (m, 2H); 7.48 (m, 6H).
3.6. N-(40-Ferrocenyl[1,10]biphenyl-4-yl)formamide (4)
3.3. Gold(I) thiophenolate (1)
A
solution of 40-ferrocenyl[1,10]biphenyl-4-amine (0.40 g;
Thiophenol (2.26 g; 20.5 mmol) was added with stirring to a
solution of hydrogen tetrachloroaurate (HAuCl4ꢀ3H2O) (2.10 g;
5.33 mmol) in methanol (61 ml) and water (12 ml). The reaction
mixture was stirred for 10 min. A white precipitate of gold thio-
phenolate (1) was separated by filtration, washed with methanol
(10 ml), acetone (10 ml), then ether (10 ml) and dried in air. Gold
thiophenolate (1), 1.60 g (98%) was obtained as a white powder;
decomp. above 178 °C. Anal. Calc. for C6H5AuS: C, 23.54; H, 1.65.
Found: C 23.71; H, 1.50%.
1.13 mmol) in 3 ml of THF was added with stirring to a cold
(ꢂ20 °C) solution of acetic formic anhydride (0.26 g; 2.93 mmol)
in 4 ml of THF. Stirring was continued for an additional 10 min
and solvent was removed in vacuo. N-(40-Ferrocenyl[1,10]biphe-
nyl-4-yl)formamide (5) (0.34 g; 79%) was obtained, decomp. above
240 °C. Anal. Calc. for C23H19FeNO: C, 72.46; H, 5.02; N, 3.67.
Found: C, 72.14; H, 4.88; N, 3.78%. 1H NMR (chloroform-d, d):
4.06 (s, 5H); 4.33 (m, 2H); 4.66 (m, 2H); 7.38 (m, 9H); 8.57 (broad
signal, 1H). IR (nujol,
(NH).
m
, cmꢂ1): 1520 (C@O), 1690 (C@O), 3200
3.4. Tris(4-ferrocenylphenyl)boroxine (2). Modified procedure [2]
A cold (ꢂ6 °C) 1.6 M n-BuLi solution (10.5 ml, 16.8 mmol) in
3.7. 40-Ferrocenyl[1,10]biphenyl-4-amine (3) – typical procedure
hexane was added to
a
solution of 4-bromophenylferrocene
To boroxine 2 (1.80 g; 0.2 mmol) in an argon purge were
sequentially added: 4-iodoaniline (0.140 g; 0.64 mmol), K2CO3
(0.220 g; 1.72 mmol), dimethylformamide (5 ml), water (3 ml)
and tetrakis(triphenylphosphine)palladium (0.230 g; 0.02 mmol).
The reaction mixture was stirred in an argon purge at 65–75 °C
for 3 h and then poured into water (50 ml). The product was
(5.0 g, 14.6 mmol) [2] in a mixture of THF (85 ml) and ether
(25 ml) cooled to ꢂ60 °C. The reaction mixture was stirred at
ꢂ60 °C for 50 min. A solution of 4-ferrocenylphenyllithium was ob-
tained (in some experiments this organolithium compound was
formed as an orange suspension). Freshly distilled tributyl borate

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V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 695 (2010) 304–309
extracted from the resulting suspension with chloroform (three
portions of 10 ml). The combined extracts were washed with sev-
eral portions of water, dried with Na2SO4 and then chloroform was
removed in vacuo. The residue was subjected to column chroma-
tography on silica gel with methylene chloride as the eluent. After
removal of the solvent in vacuo, 0.15 g (68%) of 3 was obtained,
m.p. 162–165 °C. 1H NMR (chloroform-d, d): 3.71 (s, 2H); 4.07 (s,
5H); 4.32 (m, 2H); 4.66 (m, 2H); 6.76 (m, 2H); 7.48 (m, 6H).
stirred under reflux for an additional 20 min, then cooled to ambi-
ent temperature and washed with a 10% solution of Na2CO3. The
organic layer was separated and dried over Na2SO4. The solvent
was removed on rotary evaporator and the residue was subjected
to chromatography on silica gel (eluent, 1:1 petroleum ether:chlo-
roform mixture). Isocyanide 7 was obtained (0.26 g; 81%), m.p.
169–170 °C. Anal. Calc. for C23H17FeN: C, 76.05; H, 4.72; N, 3.86.
Found: C, 76.10; H, 4.71; N, 3.86%. 1H NMR (chloroform-d, d):
4.06 (s, 5H); 4.36 (m, 2H); 4.68 (m, 2H); 7.52 (m, 8H).
3.8. N-(40-Ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-yl)formamide (4)
3.12. (40-Ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-yl)isocyanide (8)
The reaction was carried out with boroxine
2 (1.44 g;
1.7 mmol), 4-bromoformanilide (1.00 g; 5.0 mmol), K2CO3
(1.93 g; 14 mmol), dimethylformamide (45 ml), water (25 ml)
and tetrakis(triphenylphosphine)palladium (0.20 g; 0.17 mmol).
After chromatography on silica gel (eluent, 1:1 chloroform:ether
mixture) 1.34 g (70%) of 4 was obtained, decomp. above 240 °C.
1H NMR and IR spectra are consistent with spectra of an authentic
sample (see above).
A 1.25 M solution of diphosgene in chloroform (1 ml;
1.25 mmol of diphosgene) was slowly added with stirring to a
refluxing suspension of formamide 6 (1.00 g; 1.45 mmol) in a mix-
ture of dry triethylamine (2.4 ml) and chloroform (25 ml). The
reaction mixture was stirred under reflux for an additional
15 min, then it was worked up as in the case of isocyanide 7. Iso-
cyanide 8 was obtained (0.73 g; 76%) as dark red powder, m.p.
186–188 °C. Anal. Calc. for C25H21FeN: C, 76.74; H, 5.41; N, 3.58.
Found: C, 76.75; H, 5.46; N, 3.45%. 1H NMR (chloroform-d, d):
2.48 (s, 6H); 4.05 (s, 5H); 4.34 (m, 2H); 4.67 (m, 2H); 7.33 (m,
2H); 7.45–7.54 (m, 4H, AA0BB0 – system).
3.9. 40-Ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-amine (5)
3.9.1. Catalyst – Pd(PPh3)4
The reaction was carried out with boroxine
2 (0.1640 g;
0.19 mmol), 4-iodo-2,6-dimethylaniline (0.1400 g; 0.57 mmol),
K2CO3 (0.2200 g; 1.72 mmol), dimethylformamide (5 ml), water
(3 ml) and tetrakis(triphenylphosphine)palladium (0.0230 g;
0.02 mmol). After chromatography on silica gel (eluent, chloro-
form) 0.14 g (65%) of 5 was obtained, m.p. 152–154 °C. Anal. Calc.
for C24H23FeN: C, 75.60; H, 6.08; N, 3.67. Found: C, 75.70; H, 6.11;
N, 3.65%. 1H NMR (chloroform-d, d): 2.26 (s, 6H); 3.62 (s, 2H); 4.06
(s, 5H); 4.31 (m, 2H); 4.65 (m, 2H); 7.23 (s, 2H); 7.47 (m, 6H).
3.13. (Chloro)gold{(40-Ferrocenyl[1,10]biphenyl-4-yl)isocyanide} (9)
A solution of isocyanide 7 (0.04 g; 0.1 mmol) in 2 ml of THF was
added with stirring to
a
solution of (tetrahydrothio-
phene)gold(I)chloride (0.035 g; 0.1 mmol) [18] in 3 ml of THF.
The reaction mixture was stirred for 5 min then ether (4 ml) was
added and solvent was decanted from the precipitate of complex
9. The precipitate was washed with ether and air-dried.
Complex 9 was obtained (0.51 g; 77%) as an orange powder, de-
comp. above 220 °C. Anal. Calc. for C23H18AuClFeN: C, 46.38; H,
2.88; N, 2.35. Found: C, 46.28; H, 2.82; N, 3.00%.
3.9.2. Catalyst – (Ph3P)2PdCl2
The reaction was carried out as described in the previous exper-
iment. From boroxine 2 (0.52 g; 0.6 mmol) and 4-iodo-2,6-dimeth-
ylaniline (0.44 g; 1.8 mmol), compound
5
0.38 g (55%) was
3.14. (Chloro)gold{(40-ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-
obtained, m.p. 152–154 °C.
yl)isocyanide} (10)
3.10. N-(40-Ferrocenyl-3,5-dimethyl[1,10]biphenyl-4-yl)formamide (6)
The experiment was carried out as described for preparation of
complex 9. From isocyanide 8 (0.10 g (0.26 mmol) and (tetrahydro-
thiophene)gold(I)chloride (0.08 g; 0.26 mmol) complex 10 was ob-
tained (0.13 g; 80%) as an orange powder, decomp. above 220 °C.
Anal. Calc. for C25H21AuClFeN: C, 48.14; H, 3.39; N, 2.25. Found:
C, 48.30; H, 3.40; N, 2.34%.
3.10.1. Catalyst – Pd(PPh3)4
The reaction was carried out with boroxine
2 (1.04 g;
1.2 mmol), 4-iodo-2,6-dimethylformanilide (0.99 g; 3.6 mmol),
K2CO3 (1.32 g; 9.6 mmol), dimethylformamide (25 ml), water
(15 ml) and tetrakis(triphenylphosphine)palladium (0.14 g;
0.12 mmol). After chromatography on silica gel (eluent, 1:1 chloro-
form:ether mixture) 1.21 g (85%) of 6 was obtained, m.p. 170–
171 °C. Anal. Calc. for C25H23FeNO: C, 73.36; H, 5.67; N, 3.42.
Found: C, 73.46; H, 5.76; N, 3.42%. 1H NMR (chloroform-d, d):
2.34 (s, 3H); 2.38 (s, 3H); 4.06 (s, 5H); 4.34 (m, 2H); 4.67 (m,
2H); 7.36 (m, 2H); 7.48 (m, 4H); 8.13 (s, 0.5H: NH); 8.16 (s, 0.5H:
NH); 8.45 (s, 1H: CHO).
3.15. (Thiophenolato)gold{(40-ferrocenyl[1,10]biphenyl-4-
yl)isocyanide} (11)
A solution of isocyanide 7 (0.18 g; 0.5 mmol) in 5 ml of THF was
added with stirring to a suspension of gold thiophenolate (1)
(0.15 g; 0.5 mmol) in THF (10 ml). The reaction mixture was stirred
for 20 min. A white precipitate of 1 initially dissolved then an or-
ange precipitate formed. This orange precipitate was separated
by filtration, washed with petroleum ether and air-dried. Complex
11 was obtained (0.2 g; 61%) as an orange powder, m.p. 196–
198 °C, decomp. Anal. Calc. for C29H22AuFeNS: C, 52.04; H, 3.31;
N, 2.09. Found: C, 52.10; H, 3.33; N, 2.12%.
3.10.2. Catalyst – (Ph3P)2PdCl2
The reaction was carried out as described in the previous exper-
iment. From boroxine 2 (1.08 g; 1.25 mmol) and 4-iodo-2,6-dim-
ethylformanilide, compound 6 (1.12 g; 76%) was obtained, m.p.
170–171 °C.
3.16. (Thiophenolato)gold{(40-Ferrocenyl-3,5-dimethyl[1,10]biphenyl-
4-yl)isocyanide} (12)
3.11. (40-Ferrocenyl[1,10]biphenyl-4-yl)isocyanide (7)
A
0.83 M solution of diphosgene in chloroform (0.54 ml,
A solution of isocyanide 8 (0.25 g; 0.65 mmol) in 5 ml of THF
was added with stirring to a suspension of gold thiophenolate (1)
(0.25 g; 0.65 mmol) in THF (10 ml). The reaction mixture was stir-
red for 15 min, an insoluble precipitate was filtered off, and solvent
0.45 mmol of diphosgene) was slowly added with stirring to a
refluxing suspension of formamide, 4 in a mixture of dry triethyl-
amine (0.8 ml) and chloroform (3 ml). The reaction mixture was

V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 695 (2010) 304–309
309
Table 3
two components were separately included in refinement via HKLF
5 format (BASF is 0.26). All equivalent reflections for 9 were merged
using the TWINABS program.
Crystal data and structure refinement parameters for 9 and 12.
Compound
9
12
The analysis of the Fourier synthesis of the electron density in
12 revealed that one of the Cp-rings (C(6)–C(10)) and one phenyl
ring C(26)–C(31) are disordered over two positions which were re-
fined in the isotropic approximation. Hydrogen atoms were located
from the Fourier synthesis of the electron density and refined in
the riding model. All calculations were performed using the SHELXTL
PLUS 5.0.
Formula
FW
T (K)
Crystal system
Space group
Z
a (Å)
b (Å)
c (Å)
C23H17AuClFeN
595.64
100
Monoclinic
P21/c
C31H26AuFeNS
697.40
100
Monoclinic
P21/n
4 (1)
4 (1)
16.0368(7)
10.6479(7)
11.4182(9)
90.00
108.9190(10)
90.00
1844.4(2)
2.145
88.84
9.5959(9)
11.2351(12)
23.360(2)
90.00
98.146(3)
90.00
2493.0(4)
1.858
65.65
a
(°)
Acknowledgement
b (°)
c
(°)
V (Å3)
This investigation was supported by Russian Foundation Basic
Research # 08-03-00920-a.
Dcalc (g cmꢂ1
l
)
(cmꢂ1
)
F(0 0 0)
h Range (°)
1136
58
1360
56
Appendix A. Supplementary data
Reflections measured
Independent reflections
Observed reflections [I > 2
Number of paramaters
Final R(Fhkl): R1
7150
7178
5540
245
0.0613
0.1962
1.066
2.21, ꢂ1.55
27 533
6005
5439
CCDC 736698 and 736697 contains the supplementary crystal-
lographic data for 9 and 12. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2009.09.043.
r
(I)]
309
0.0282
0.0647
1.092
1.09, ꢂ0.88
wR2
GOF
D
qmax
,
D
qmin (e Åꢂ3
)
References
was removed in vacuo. Complex 12 was obtained (0.27 g; 60%) as a
red powder, m.p. 180–183 °C, decomp. Anal. Calc. for C31H26Au-
FeNS: C, 53.39; H, 3.76; N, 2.01. Found: C, 53.13; H, 3.80; N,
2.20%. 1H NMR (chloroform-d, d): 2.50 (s, 6H); 4.05 (s, 5H); 4.34
(m, 2H); 4.68 (m, 2H); 7.01 (m, 1H); 7.12 (m, 2H); 7.47 (m, 8H).
[1] A.E. Bruce, M.R.M. Bruce, S.A. Larkin, D. Lemenovskii, V. Dyadchenko, K.
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3.17. X-ray structures
Crystals of 9 were grown by gradual addition of ether to a solu-
tion of 9 in THF. Crystals of 12 were obtained by crystallization of
the complex from hot toluene. All diffraction data were taken using
a Bruker SMART APEX II CCD diffractometer [k(Mo Ka) = 0.71072 Å,
x
-scans] (see Table 3). The substantial redundancy in data allows
empirical absorption correction to be applied using multiple mea-
surements of equivalent reflections with SADABS. The structures
were solved by direct methods and refined by the full-matrix
least-squares technique against F2 in the anisotropic-isotropic
approximation.
The results of the index procedure as well as visual inspection of
the three-dimensional and rocking curves of spots revealed that
the crystal of 9 was a growth twin. All attempts to find a non-
twinned sample, even with extremely small dimensions, were
unsuccessful since it appears that all crystals were obtained as
twins. The collected dataset was indexed using cell_now software
and then intensities of the collected reflections were described as
superpositions of two crystal components with a rotation angle
equal to 179.5° along the (0 0 1) direction. The frames for 9 were
integrated separately for each component and then reflections of
[13] L.I. Krimen, Org. Synth. 50–9 (1988) 8–9.
[14] R.Q. Brewster, Org. Synth. 2 (1943) 347–348.
[15] T.F. El-Moselhy, M.A. El-Kersh, F. Nyberg, R. Hede, M.A. Eldawy, Med. Chem.
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Akademii Nauk, Seriya Khimicheskaya), Russ. Chem. Bull. 52 (2003) 607–615.
[18] (Tetrahydrothiophene)gold(I)chloride was prepared by reduction of
tetrachloroauric acid with excess bis(2-hydroxyethyl)sulfide in water-
ethanol solution, followed by addition of excess tetrahydrothiophene. The
precipate was filtered, washed with water, ethanol, acetone, ether, and dried.
Yield (84%) Anal. calc. for C4H8ClAuS: C, 14.99; H, 2.52; S, 10.00. Found C,
14.98; H, 2.50; S, 9.19%.