Chiral phosphine ligands in the structural chemistry of gold

Article abstract of DOI:10.1515/znb-1997-1207

The reaction of chloro(dimethylsulfide)gold(I) with (2-hydroxybutyl)diphenylphosphine (L) (racemic mixture) in dichloromethane affords high yields of the racemic chiral complex (L)AuCl. Metathesis reactions with KBr or KI, respectively, in a two-phase solvent mixture (CH₂C1₂/H₂O) lead to a conversion into the corresponding bromide and iodide complexes (L)AuBr and (L)AuI. Treatment of silver chloride with the ligand L in acetonitrile yields the analogous 1:1 adduct (L)AgCl. The compounds have been characterized by their analytical and spectroscopic data, and the structures of (L)AuCl and (L)AuBr have been determined by single-crystal X-ray diffraction. The compounds build isomorphous crystal lattices (monoclinic, P2₁/c) in which pairs of enantiomers (R- and S-configuration of L) are aggregated by two long hydrogen bonds between the hydroxyl group of the ligand and the halogen substituent of the neighbouring molecule. Cationic, linear two-coordinate 1:2 complexes (L)₂Au⁺ X^- (X = BF₄, ClO₄, SO₃CF₃) and (L)₂Ag⁺ X^- (X = BF₄) are obtained in good yields by reaction of L with Me₂SAuCl and AgX (molar ratio 2:1:1) or with AgBF₄ (molar ratio 2:1), respectively. ³¹P NMR studies at variable temperature show an equilibrium between all possible stereoisomers (RR, SS, RS, SR) in solution with rapid ligand exchange at ambient temperatures.

Full text of DOI:10.1515/znb-1997-1207

Chiral Phosphine Ligands in the Structural Chemistry of Gold
Angela Bayler, Andreas Bauer, Hubert Schmidbaur*
Anorganisch-chemisches Institut der Technischen Universität München,
Lichtenbergstrasse 4, D-85747 Garching, Germany
Z. Naturforsch. 52 b, 1477-1483 (1997); received October 14, 1997
Gold Complexes, Phosphane Complexes, Chiral Phosphanes, Crystal Structure, Diastereomers
The reaction of chloro(dimethylsulfide)gold(I) with (2-hydroxybutyl)diphenylphosphine (L)
(racemic mixture) in dichloromethane affords high yields of the racemic chiral complex
(L)AuCl. Metathesis reactions with KBr or KI, respectively, in a two-phase solvent mix-
ture (CH2CI2/H2O) lead to a conversion into the corresponding bromide and iodide complexes
(L)AuBr and (L)AuI. Treatment of silver chloride with the ligand L in acetonitrile yields the
analogous 1:1 adduct (L)AgCl. The compounds have been characterized by their analytical
and spectroscopic data, and the structures of (L)AuCl and (L)AuBr have been determined by
single-crystal X-ray diffraction. The compounds build isomorphous crystal lattices (monoclinic,
P2i/c) in which pairs of enantiomers (R- and S-configuration of L) are aggregated by two long
hydrogen bonds between the hydroxyl group of the ligand and the halogen substituent of the
neighbouring molecule. Cationic, linear two-coordinate 1:2 complexes (L)2Au+ X- (X = BF4,
CIO4, SO3CF3) and (L)2Ag+ X- (X = BF4) are obtained in good yields by reaction of L with
Me2SAuCl and AgX (molar ratio 2:1:1) or with AgBF4 (molar ratio 2:1), respectively. 31P
NMR studies at variable temperature show an equilibrium between all possible stereoisomers
(RR, SS, RS, SR) in solution with rapid ligand exchange at ambient temperatures.
Introduction
and therefore we have undertaken a preparative and
structural study of a few representative model sys-
tems using a tertiary phosphine with an asymmet-
rically substituted carbon atom (a "center of chiral-
ity") in one of the organic substituents of the ligand.
Phosphine ligands play a key role in the coor-
dination chemistry of gold in its lower oxydation
state Au(I). Many of the compounds used for the
most important applications of gold in contempo-
rary medicine and technology are phosphine com-
plexes [1]. The primary, secondary or tertiary phos-
phine donor functions in mono- or polydentate lig-
ands are superior to most other ligands and lead to
the most stable complexes which adopt a linear two-
coordinate structure in standard cases. The unusual
structural chemistry of many gold(I) complexes is
based on non-classical inter- and intramolecular
Au(I)-Au(I) contacts [2]. In their bond energy, these
interactions between seemingly closed-shell metal
centers (5d10), arising mainly from relativistic and
correlation effects [3], are comparable to hydrogen
bonds [4]. Surprisingly, the effect of chirality of
phosphine ligands on the chemical properties and
structure has not been probed in more than a few
sporadic cases [5].
Both 1:1 and 1:2 complexes were included in or-
der to obtain enantiomers and diastereomers of this
most simple type of metal coordination (linear two-
coordinate). Analogous silver(I) complexes have
also been considered, because NMR spectroscopy
is more informative with this lighter coinage metal
with its two spin 1/2 isotopes. It was also antici-
pated that the presence of a hydroxyl group at the
chiral ligand would lead to a directional influence
on the solid state structure through the build-up of
hydrogen bonds supporting the aggregation through
other forces like aurophilicity [7],
Synthesis and Structure of 1:1 Complexes
A racemic mixture of (2-hydroxybutyl)diphenyl-
phosphine (L) was chosen as a ligand prototype
with a center of chirality in its alkyl substituent and
with a hydroxyl group as one of the functions at the
asymetrical carbon atom. This compound is read-
ily prepared from potassium diphenylphosphide and
Stereoisomerism at two-coordinate metal atoms
is generally not a very common phenomenon [6],
* Reprint requests to Prof. Dr. H. Schmidbaur.
0939-5075/97/1200-1477 $ 06.00 (c) 1997 Verlag der Zeitschrift für Naturforschung. All rights reserved.
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A. Bayler et al. • Chiral Phosphine Ligands in the Structural Chemistry of Gold
1478
C4'
Fig. 1. Molecular structures of
compounds (L)AuCl (a) and
(L)AuBr (b).(ORTEP draw-
ing with 50% probability el-
lipsoids, C//-atoms are omit-
ted for clarity). Selected bond
lengths [A] and angles [°]:
(a): Au-Cl 2.2973(13),
Au-P 2.2285(13);
Cl-Au-P 176.03(5);
O-H 1.077,
Br
H- • Cl' 2.347,
O-H-- Cl' 161.3;
(b); Au-Br 2.4129(9),
Au-P 2.232(2);
Br-Au-P 176.33(6);
O-H 1.035;
H- ■Br’2.535;
O-H- • Br’ 152.5.
Br'
1 ,2 -epoxy-butane following a modified literature with only slight variations in the chemical shifts
procedure [8] and may also serve as synthon to and coupling constants as a function of the nature
prepare further functionalized chiral phosphines or of the halogen co-ligand. The influence of the metal
diphosphines.
atoms is much greater as shown by the differences
between the data for the AuCl and AgCl complexes
(Exp. Part). Owing to the neighbouring center of
chirality, the two phenyl groups at the phosphorus
atom are diastereotopic and give two sets of 13C
resonances. The non-equivalence of the hydrogen
atoms of each of the two CH2 groups leads to the
expected multiplicity in the 1H spectra.
Treatment of chloro(dimethylsulfide)gold(I) with
this ligand
L
in the molar ratio 1:1 in
dichloromethane affords high yields of the expected
1:1 complex (L)AuCl as colourless crystals (91%,
m.p. 152°C). This product is readily converted into
the corresponding bromide and iodide complexes,
(L)AuBr and (L)AuI, in metathesis reactions with
KBr or KI, respectively, in a two-phase system
(H20/CH2C12; yields 85/81%, m.p. 140/109°C).
In CDCI3 at 25°C, the complex (L)AgCl shows no
splitting of the 31P resonance by the spin 1/2 nuclei
of the two silver isotopes 107Ag and 109Ag, prob-
ably owing to a rapid ligand exchange. At -90°C
complex sets of resonances with multiplet patterns
appear, which suggest that not only a simple ligand
The analogous 1:1 complex with silver chloride,
(L)AgCl, is obtained by reacting freshly prepared,
dry AgCl with the ligand L in acetonitrile (62%
yield, m.p. 165°C).
All four 1:1 complexes are air-stable solids, solu- exchange, but also a complex oligomerisation equi-
ble in tetrahydrofuran and di- or trichloromethane.
In the NMR spectra, the resulting solutions show
librium (with mainly dimers and various tetrameric
forms) are contributing to the processes involved.
the expected sets of *H, 31P and l3C resonances There is extensive literature on the various forms of
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1479
A. Bayler et al. • Chiral Phosphine Ligands in the Structural Chemistry of Gold
aggregates of (phosphine)silver halides which are
mainly determined by the steric and electronic ef-
fect of the ligands [9]. No attempt was made to
clarify this aspect for the present example (L)AgCl.
Crystals grown from various solvents turned out to
be twinned in all cases.
In the mass spectra (FAB) of the gold complexes
the molecular ions [(L)AuX]+ are present in low
intensity. The halogenonium ions {[(L)Au]2X}+are
detected as the ions of highest mass (X = Cl, Br, I;),
and the ions [(L)Au]+ are the most abundant. This
result confirms earlier reports on the high stability of
digold(I) halogenonium cations with their A-shaped
structure where the horizontal bar represents Au-Au
bonding [10 ].
Single crystals of (L)AuCl and (L)AuBr are ob-
tained by careful layering of solutions in CH2CI2
with pentane. The crystals are isomorphous, mon-
oclinic, space group P2j/c, with four formula units
in the unit cell. In the lattices, the two enantiomers
(containing the R- or S-configuration of the ligand)
appear in pairs, the components of which are related
by acenter of inversion (Figures 1a, b). The only dis-
cernible bonding relations between the enantiomers
are two long hydrogen bonds extending from the
hydroxyl groups of the ligand to the halogen atoms
of the neighbouring molecule.
The bond lengths and angles of the monomers are
within the range of standard data in the literature
for L-Au-X molecules with phosphine and halogen
ligands (captions to Figures la, b).
Of the iodine homologue, (L)AuI, no single crys-
tals could be grown.
Fig. 2. Temperature-dependent 31P NMR spectra of
[(L)2Au]+ BF4- (a) and [(L)2Ag]+ BF4~ (b).
Synthesis, Spectroscopy and Isomerism of the 2:1
Complexes
The four 2:1 complexes are colourless, air-stable
crystalline solids with excellent solubility in alco-
hols, tetrahydrofuran, and di- or trichloromethane.
The NMR spectra of solutions in chloroform at
room temperature are similar to those of the 1:1
compounds (above) reflecting the chirality of the
ligands.
Treatment of Me2SAuCl with two equivalents of
the ligand L in the presence of one equivalent of
AgBF4 in a mixture of dichloromethane and tetrahy-
drofuran leads to a precipitate of AgCl, and the su-
pernatant solution contains the complex [(L)2Au]+
BF4- (87% yield, m.p. 69°C). With AgCl54 or
Ag0 S0 2 CF3 instead of AgBF4 the corresponding
perchlorate and triflate salts are obtained, respec-
tively.
Again, the 31P spectra give singlet resonances
at 25°C due to rapid ligand exchange. Already at
-40°C (for the silver compound at -60°C), however,
The reaction of AgBF4 with two mole equivalents these signals are split into two resonances (of equal
of L in tetrahydrofuran gives the complex [(L)2Ag]+ intensity) for the three gold compounds, and into
BF4_ in 96% yield, m.p. 108°C.
two doublets of doublets for the silver compound
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1480
A. Bayler et al. ■Chiral Phosphine Ligands in the Structural Chemistry of Gold
(Figures 2a, b). This splitting has its origin in the
presence of the four diastereomeric cations [R,R]+,
[S,S]+, [R,S]+, and [S,R]+, in which the phosphorus
atoms are either related by a center of inversion or
by a mirror plane.
6 = 0.97 (t,
V
h . h = 7.4 Hz, 3H) CH3; 1.66 (m, 2H) CH2-
CH3; 1.95 (br. s, 1H) OH; 2.56 (ddd, 2/ h ,h = 14.6 Hz, 2/ H p
= 10.7 Hz, -VHih = 3.3 Hz, 1H), 2.77 (ddd, 27h,h = 14.6
H z,2Jh.? = 11-0 Hz, 3/ h ,h = 9.2 Hz, 1H) CH2-P; 4.1 1(m ,
1H) CH; 7.37 - 7.78 (m, 10 H) arene H. - 13C{'H} NMR:
6 = 9.7 (s) CH3; 31.9 (d, -Vc,p = 11.6 Hz) CH2-CH3; 36.1
(d, ’/c.p = 38.9 Hz) CH2-P; 71.0 (d, 2JC,P = 2 Hz) CH;
129.1 (id, 37c,p = 12.0 Hz), 129.3 (d, 37c,p = 11.6hz)c 3/5;
129.8 (d, '7c,p = 58.6 Hz), 130.0 (d, '7c,P = 61.2 Hi) C,;
131.8 (d, 4Jc,p = 2.5 Hz), 131.9 (d, 47c,p = 2.5 Hz) C4;
133.2 (d, 2J c ,p = 12.0 Hz), 133.3 (d, 27c,p = 12.0 Hz) C2/6.
- 31P{'H} NMR: 6 = 25.9 (s). - MS (FAB), m/z (%): 947
(16) {[(L)Au]237Cl}+, 945 (42) {[(L)Au]235C1}+, 490 (2)
[(L)AuCl]+, 455 (100) [(L)Au]+.
These signals split further into doublets of dou-
blets for the silver compound through coupling with
the two isotopic silver nuclei (109Ag, 107Ag). The
coupling constants J(P-Ag) are in the ratio of the gy-
romagnetic factors (1.15). Upon warming to 30°C
coalescence of the signals occurs owing to the in-
creasing ligand exchange rates.
Both in the coalesced spectrum at the high tem-
perature limit and at -50°C the proton resonance of
the OH groups is detected at remarkably low field
suggesting strong intra- or intermolecular hydrogen
bonding. It is conceivable that the proximity of the
ligands in the 2:1 complexes favours the close ap-
proach necessary for interactions between hydroxyl
groups. Unfortunately, no single crystals could be
obtained from any of the four 2:1 compounds. All
predictions regarding the structure therefore remain
only tentative.
[R/S-(2-Hydroxybutyl)diphenylphosphine]gold(I)-
bromide
15 ml of an aqueous solution of KBr (1.0 g, ex-
cess) was added to a solution of (L)AuCl (98 mg, 0.2
mmol) in 15 ml of CH2C12. The resulting two-phase
system was stirred vigorously for 5 h, upon which the
aqueous layer was separated and washed with 10 ml of
CH2C12. The dichloromethane extracts were combined,
dried with MgS04, and the solvent was evaporated un-
der vacuum to leave a white crystalline product. Single
crystals suitable for X-ray diffraction were obtained from
dichloromethane/pentane at room temperature; yield 91
Experimental Part
mg (85%), m.p. 140 °C. - 'H NMR: 6 = 0.92 (t, 3/ h , h
=
All experiments were carried out under dry, purified
nitrogen. Solvents were dried, distilled and stored over
molecular sieves in a nitrogen atmosphere. Glassware was
ovendried, evacuated and filled with nitrogen.
7.4 Hz, 3H) CH3; 1.61 (m, 2H) C//2-CH3. 1.75 (br. s, 1H)
OH; 2.51 (ddd, 27h,h = 14.7 Hz, 27h,p = 10.4 Hz, 37h,h
= 3.3 Hz, 1H), 2.77 (ddd, 27h,h = 14.7 Hz, 2/ h,p = 11.0
Hz, Vh.h = 9.1 Hz, 1H) CH2-P; 4.09 (m, 1H) CH; 7.37
- 7.78 (m, 10 H) arene H. - ,3C{’H} NMR: <5= 9.7 (s)
CH3; 31.9 (d, -Vc,p =11-0 Hz) CH2-CH3; 36.3 (d, VC,P
= 37.7 Hz) CH2-P; 71.9 (d, 2/ c,p = 2 Hz) CH; 129.1 (d,
3/c,p = 12.0 Hz), 129.3 (d, 3/ c ,p = 12.0 Hz) C3/5; 130.0
(d, ‘7 c ,p = 59.8 Hz), 130.2 (d, ]JC,P = 58.8 Hz) Q ; 131.8
(d, 4/ c ,P = 2.8 Hz), 131.9 (d, 4/ c,p = 2.8 Hz) C4; 133.2
Racemic (2-hydroxybutyl)diphenylphosphine was
prepared according to a modified literature procedure
by reaction of potassium diphenylphosphide with 1,2-
epoxybutane followed by hydrolysis [8],
NMR: Jeol GX 400, Jeol JNM-LA400; CDCI3 as sol-
vent and internal standard, converted to TMS for 1H and
13C{1H}; H3PO4 (85%) as external standard for 31P{' H};
spectra were measured at room temperature, unless noted
otherwise. - MS: Finnigan MAT 90 (fast atom bombard-
ment).
(d, 2/ c,p = 11.0 Hz), 133.3 (d, 27 c ,p
=
11.0 Hz) C2/6. -
3,P{'H} NMR: 6 = 28.5 (s). - MS (FAB), m/z (%): 991
(24) {[(L)Au]281Br}+, 989 (23) {[(L)Au]279Br}+, 536 (6)
[(L)Au81Br]+, 534 (6) [(L)Au79Brl, 455 (100) [(L)Au]+.
[R/S-(2-Hydroxybutyl)diphenylphosphine]gold(I)-
chloride
[R/S-(2-Hydroxybutyl)diphenylphosphine]gold(I)-iodide
(2-Hydroxybutyl)diphenylphosphine (263 mg, 1.0
mmol) and Me2SAuCl (300 mg, 1.0 mmol) were dis-
solved in 10 ml of CH2CI2 to give a clear colourless
Following the procedure given above using 1.0 g of KI
and 147 mg (0.3 mmol) of (L)AuCl; yield 141 mg (81%),
m.p. 109 °C. - ‘H NMR: 6 = 0.88 (t, 37 h ,h = 7.3 Hz, 3H)
solution, which was stirred for 1 h at ambient tempera- CH3; 1.57 (m, 2H) C//2-CH3; 1.80 (br. s, 1H) OH; 2.49
ture. Careful layering of the solution with pentane precip-
itated the product as colourless crystals suitable for X-ray
diffraction; yield 455 mg (91 %), m.p. 152 °C. - 1H NMR:
(ddd, 2/ h .h = 14.6 Hz, 27 h ,p = 11.0 Hz, 3/ h ,h = 2.9 Hz,
1H), 2.70 (ddd, 2/ h ,h = 14.6 Hz, 27 h ,p = 11.0 Hz, 3/ h .h
= 9.5 Hz, 1H) CH2-P; 4.04 (m, 1H) CH; 7.35 - 7.80 (m,
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1481
A. Bayler et al. ■Chiral Phosphine Ligands in the Structural Chemistry of Gold
was filtered off and the solvent was evaporated under vac-
uum to leave a white, crystalline product; yield 210 mg
10 H) arene H. - 13C{*H} NMR: 6 = 9.7 (s) CH3; 31.9
(d, 3/ c,p = 11.6 Hz) CH2-CH3; 36.6 (d, ]Jc,p = 35.6 Hz)
CH2-P; 70.6 (d, 2JC,P = 2 Hz) CH; 129.1 (d, 37 c ,p = 12.0
Hz), 129.3 (d, 3/ c ,p =11.6 Hz) C3/5; 130.4 (d, lJc<P= 57.5
Hz), 130.5 (d, '7c,p = 57.5 Hz) Q ; 131.7 (d, 4/ c,p = 2.5
Hz), 131.8 (d, 47c!p = 2.5 Hz) C4; 133.2 (d, 2JC,p = 13.6
Hz), 133.2 (d, 27 c ,p = 13.6 Hz) C2/6. - 3iP{'H} NMR: 6
(87%), m.p. 69 °C. - ‘H NMR:
6
= 0.86 (t, 3/ h ,h = 7.3
Hz, 3H) CH3; 1.57 (m, 2H) CH2-CH3; 2.72 (br. d, 1H),
2.84 (br. dd, 1H) CH2-P; 3.66 (m, 1H) CH; 4.23 (br. s,
1H) OH; 7.38 - 7.72 (m, 10 H) arene H. - 31P{'H} NMR
(25 °C): 6 = 35.7 (s); (- 40 °C): 6A = 35.1 (s), 6B = 35.2
= 31.9 (s). - MS (FAB), m/z (%): 1037 (16) {[(L)Au]2I}+, (s). - MS (FAB), m/z (%): 713 (100) [(L)2Au]+, 455 (16)
[(L)Au]+. The corresponding perchlorate and triflate salts
can be obtained in an analogous way. The products give
the same lH NMR, 31P{'H} NMR and FAB-MS spectra
as reported above.
582 (8) [(L)AuI]+, 455 (43) [(L)Au]+.
Ci6Hi9AuIOP (582.21)
Calcd C 33.01 H 3.29 Au 33.84 %;
Found C 32.99 H 3.35 Au 34.0 %.
Bis[(2-hydroxybutyl)diphenylphosphine]silver(I)
tetrafluoroborate
[R/S-(2-Hydroxybutyl)diphenylphosphine]silver(I)-
chloride
A solution of AgBF4 (68 mg, 0.35 mmol) in 5
AgCl (60 mg, 0.4 mmol) was added to a solu- ml of THF was added dropwise to a solution of (2-
hydroxybutyl)diphenylphosphine (180 mg, 0.7 mmol) in
10 ml of THF with constant stirring. Stirring of the so-
tion of (2-hydroxybutyl)diphenylphosphine (105 mg, 0.4
mmol) in 20 ml of acetonitrile and the resulting sus-
pension was stirred under reflux for 6 h with protec- lution was continued for 2 h at ambient temperature, and
tion against incandescent light. The hot solution was the solvent was removed under vacuum to give the de-
sired product in the form of a white, crystalline solid;
yield 239 mg (96%), m.p. 108 °C. - 'H NMR: 6 = 0.86
( t, 3i H ,H = 7.3 Hz, 3H) CH3; 1.56 (m, 2H) CH2-CH3; 2.52
(d, 2H), CH2-P; 3.54 (m, 1H) CH; 3.90 (br. s, 1H) OH;
7.18 - 7.60 (m, 10 H) arene H. - 31P{'H} NMR (-60
°C): 6a = 0.48 (2d, lJP,Ag = 604.4 and 523.3 Hz), SB =
0.62 (2d, '/p.Ag = 602.4 and 522.3 Hz). - MS (FAB), m/z
filtered and the volatiles were removed from the fil-
trate in a vacuum. Recrystallisation of the residue from
dichloromethane/pentane afforded the desired product as
white crystalline solid; yield 100 mg (62%), m.p. 165 °C.
- ‘H NMR: 6 = 0.78 (t, 3/ h ,h = 7.3 Hz, 3H) CH3; 1.43
(m, 2H) Ctf2-CH3; 2.33 (ddd, 27h,h = 14.1 Hz, 27h,p =
10.9 Hz, 3/ h ,h = 2.7 Hz, 1H), 2.46 (ddd, 27 h ,h = 14.1
Hz, 2/ h ,p
=
10.3 Hz, 3/ h ,h = 5.2 Hz, 1H) CH2-P; 3.86 (%):626 (90) [(L)2109Ag]+, 624 (94) [(L)2107Ag]+, 367
(m, 1H) CH; 4.32 (br. s, \H) OH; 7.18 - 7.60 (m, 10 H) (86) [(L)109Ag]+, 365 (100) [(L)107Ag]+.
arene H. - 13C{'H} NMR: 8 = 10.0 (s) CH3; 32.1 (d, 3/ c,p
= 10.3 Hz) CH2-CH3; 37.0 (d, 1J c ,p = 17.0 Hz) CH2-P;
69.4 (d, 27 c ,p = 6.6 Hz) CH; 128.7 (d, 37 c ,p = 9.5 Hz),
128.9 (d, 3/ c,p = 9.9 Hz) C3/5; 129.7 (s), 130.4 (s) C4;
132.6 (d, 2Jc,p = 15.7 Hz), 133.7 (d, 27c,p = 16.5 Hz)
C2/6; 132.7 (d, !7c,p = 27.7 Hz), 133.8 (d, 'Jc.p = 28.3
Hz) C,. - 31P{‘H} NMR: 6 = -1.9 (s). - MS (FAB), m/z
(%): 912 (10) [(L)2Ag3Cl2]+, 768 (65) {[(L)Ag]2Cl}+,
626 (76) [(L)2109Ag]+, 624 (82) [(L)2107Ag]+, 367 (87)
[(L)109Ag]+, 365 (100) [(L)107Ag]+.
Crystal structure determinations
Specimens of suitable quality and size of the com-
pounds were mounted in glass capillaries and used for
measurements of precise cell constants and intensity data
collection on an Enraf Nonius CAD4 diffractometer (Mo-
Ka radiation, A(Mo-ATa ) = 0.71073 A ). During data col-
lection, three standard reflections were measured period-
ically as a general check of crystal and instrument sta-
bility. No significant changes were observed for either
compound. Lp correction was applied and intensity data
were corrected for absorption effects. The structures were
solved by direct ((L)PAuBr) and Patterson ((L)PAuCl)
methods, respectively (SHELXS-86) and completed by
full-matrix least squares techniques against F2(SHELXL-
93). The thermal motion of all non-hydrogen atoms was
treated anisotropically. All C-H atoms were placed in
C16H,9AgC10P (401.62)
Calcd C 47.85 H 4.77 %;
Found C 47.87 H 4.80 %.
Bis[(2-hydroxybutyl)diphenylphosphine]gold(I) tetraflu-
oroborate
(2-Hydroxybutyl)diphenylphosphine (155 mg, 0.6 idealized calculated positions and allowed to ride on
their corresponding carbon atoms with fixed isotropic
contributions (UjS0(fix) = 1.5 x Ueq of the attached C
atom), whereas the O-H atoms were located and re-
fined with isotropic contributions. Further information on
mmol) and Me2SAuCl (88 mg, 0.3 mmol) were dissolved
in 10 ml of CH2C12 and a solution of AgBF4 (58 mg, 0.3
mmol) in 5 ml of THF was added dropwise at ambient
temperature with stirring. After 1 h the AgCl precipitate
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1482
A. Bayler et al. ■Chiral Phosphine Ligands in the Structural Chemistry of Gold
Table I. Crystal data, data col-
[Ph2(C4H8OH)P]AuBr
[Ph2(C4H8OH)P]AuCl
lection, and structure refinement
for compounds (L)AuCl and
(L)AuBr.
Crystal data
Formula
Mr
Crystal system
Space group
a (A)
b (A)
c ( A)
Q(°)
CiöHigAuClOP
490.70
monoclinic
P 2\/c
11.935(1)
11.416(1)
11.909(1)
90
C^HigAuBrOP
535.16
monoclinic
P 2,/c
12.129(2)
11.574(1)
11.808(2)
90
95.02(1)
90
1651.3(4)
2.153
lal R = r(IIF0l - IFcll)/riFol;
[bl wR2 =
{[Ew(Fl-F2c)2VE[w(Fl)2VsX/2\
w = M[<72{F20) + (ap)2 + bp];
P = {F2 + 2Fc)/3;
a = 0.0361 ((L)AuCl), 0.0946
((L)AuBr);
95.24(1)
90
1602.1(2)
P C )
7 O
V (A )
b
=
5.313 ((L)AuCl), 5.331
((L)AuBr).
2.034
Pcaic (gem-3)
Z
4
4
F(000)
H( Mo Ka) (cm-1)
1008
114.19
936
94.42
Data collection
T(°C)
-74
-68
Scan mode
hkl range
in)
LJ
-15—+0, 0—14,-14—>14
-15—>0, 0 ^1 4 ,-1 4 ^1 5
0.64
3424
0.64
3464
sin((9/A)max (A~1)
Measured reflections
Unique reflections
3322 [Am = 0.0130]
3322
3297 [flint = 0.0123]
Refls. used for refinement 3297
Absorption correction
Tmin /7'max
spi-scans
0.43/0.99
spi-scans
0.17/0.99
Refinement
184
1/18
Refined parameters
H Atoms (found/calcd.)
Final R values [I >2cr(I)]
R l[a]
185
1/18
0.0280
0.0436
wR2[b]
0.0681
0.1187
<0.001
1.485/-2.121
<0.001
2.206/-2.132
(shift/error)max
Pfin(max7min) (eA-3)
crystal data, data collection and structure refinement are Acknowledgements
summarized in Table I. Important interatomic distances
This work was supported by the Deutsche Forschungs-
gemeinschaft, the Fonds der Chemischen Industrie and -
through the donation of chemicals - by Degussa AG and
Heraeus GmbH. The authors thank Mr. J. Riede for es-
tablishing the X-ray data sets.
and angles are shown in the corresponding Figure Cap-
tion. Anisotropic thermal parameters, tables of distances
and angles, and atomic coordinates have been deposited
with Fachinformationszentrum Karlruhe, Gesellschaft für
wissenschaftlich-technische Information mbH, D-76344
Eggenstein-Leopoldshafen. The data are available on re-
quest on quoting CSD No. 407794 and 407795.
[3] a) P. Pyykkö, Chem. Rev. 88, 563 (1988);
b) N. Kaltsoyannis, J. Chem. Soc., Dalton Trans.
1997, 1.
[4] H. Schmidbaur. W. Graf, G. Müller, Angew. Chem.,
Int. Ed. Engl. 27,417 (1988).
[1] R. J. Puddephatt, The Chemistry of Gold, p. 51, El-
sevier, Amsterdam (1978).
[2] a) H. Schmidbaur, Gold Bull. 23, 11 (1990);
b) H. Schmidbaur, Chem. Soc. Rev. 24, 391 (1995);
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A. Bayler et al. ■Chiral Phosphine Ligands in the Structural Chemistry of Gold
1483
[8] E. N. Tsvetkov, N. A. Bondarenko, I. G. Malakhova,
M. I. Kabachnik, Synthesis 1986, 198.
[9] R. J. Lancashire, in G. Wilkinson (ed.): Comprehen-
sive Coordination Chemistry, Vol. 5, p. 798, Perga-
mon: Oxford (1987).
[10] a) P. G. Jones, G. M. Sheldrick, Acta Crystallogr.
B36, 1486(1980);
[5] a) K. Angermaier, A. Sladek. H. Schmidbaur, Z.
Naturforsch. 51 b, 1671 (1996);
b) J.-C. Shi, X.-Y. Huang, D.-X. Wu, Q.-T. Liu,
Inorg. Chem. 35, 2747 (1996);
c) J.-C. Shi, B.-S. Kang, T. C. W. Mak, J. Chem.
Soc., Dalton Trans. 1997, 2171.
[6] A. Bayler, G. A. Bowmaker, H. Schmidbaur, Inorg.
Chem. 35, 5959(1996).
[7] a) W. Schneider, A. Bauer, H. Schmidbaur,
Organometallics 15, 5445 (1996);
b) R. Uson, A. Laguna, M. V. Castrillo, Synth. React.
Inorg. Met.-Org. Chem. 9, 317 (1979);
c) A. Bayler, A. Bauer, H. Schmidbaur, Chem. Ber.
130, 115(1997).
b) C. Hollatz, A. Schier, H. Schmidbaur, J. Am.
Chem. Soc. 119, 8115 (1997).
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