Diphenyl(2-hydroxy-phenyl)phosphine and its trimethylsilyl ether as ligands for Gold(I) complexes

Article abstract of DOI:10.1515/znb-1999-0109

Diphenyl(2-hydroxy-phenyl)phosphine was introduced as a ligand for gold(I) halides and pentafluorophenyl gold(I) in order to probe the interplay of intra-and intermolecular interactions based on aurophilic (Au...Au) and hydrogen bonding. 1:1 complexes of the type Ph₂(2-HO-C₆H₄)P-Au-X with X = Cl, Br, C₆F₅ have been prepared and characterized by analytical and spectroscopic data. The crystal structure of the chloro complex (1) has been determined. In the lattice the molecules form dimers through O-H...Cl hydrogen bonds. Au...Au contacts are ruled out by steric congestion. Reaction of 1 with triethylamine yields a 1:1 adduct with O-H...NEt₃ hydrogen bonding. The trimethylsilyl ether of the title ligand also forms 1:1 complexes with AuCl, AuBr, AuI, and AuC₆F₅. The crystal structures of the chloro (5) and iodo (7) compound have been determined. In both cases the lattices are built from monomers which show only minor differences in their conformations. The silylether groups are not acting as intra-or intermolecular donor functions to the gold atoms.

Full text of DOI:10.1515/znb-1999-0109

Diphenyl(2-hydroxy-phenyl)phosphine and its Trimethylsilyl Ether
as Ligands for Gold(I) Complexes
Christian Hollatz, A nnette Schier, H ubert Schm idbaur*
Anorganisch-chemisches Institut der Technischen Universität München.
Lichtenbergstrasse 4, D-85747 Garching, Germany
Z. Naturforsch. 54 b, 30-37 (1999); received November 19, 1998
Gold(I) Complexes, Phosphine Ligands, Diphenyl(2-hydroxy-phenyl)phosphine, Hydrogen
Bonding, Trimethylsilyl Ether
Diphenyl(2-hydroxy-phenyl)phosphine was introduced as a ligand for gold(I) halides and
pentafluorophenyl gold(I) in order to probe the interplay of intra- and intermolecular interactions
based on aurophilic (Au- • -Au) and hydrogen bonding. 1:1 complexes of the type Ph:(2-HO-
CftH^P-Au-X with X = Cl, Br, C6F5 have been prepared and characterized by analytical and
spectroscopic data. The crystal structure of the chloro complex (1) has been determined. In
the lattice the molecules form dimers through O-H • Cl hydrogen bonds. Au- • Au contacts
are ruled out by steric congestion. Reaction of 1 with triethylamine yields a 1:1 adduct with
O-H • -NEt, hydrogen bonding. The trimethylsilyl ether of the title ligand also forms 1:1
complexes with AuCl, AuBr, Aul, and AuC6F5. The crystal structures of the chloro (5) and
iodo (7) compound have been determined. In both cases the lattices are built from monomers
which show only minor differences in their conformations. The silylether groups are not acting
as intra- or intermolecular donor functions to the gold atoms.
Introduction
chem istry of the title ligand with other transition el-
em ents [ 10].
Linear tw o-coordinate gold(I) com plexes L-Au-
show very special interm olecular interactions
X
Preparation and Characterization of the
Complexes
w hich often give rise to novel supram olecular struc-
tures based on Au- ••Au (aurophilic) bonding [1 - 3].
If suitable functional groups are provided, these in-
teractions are com plem ented by standard coordina-
tive or - m ost im portantly - hydrogen bonding to
give robust extended structures [4 -6 ]. W ith certain
geom etrical restraints, the interm olecular bonding
can also lead to more lim ited, package-like entities
[7 - 9],
Treatm ent of chloro(dim ethylsulfide)gold(I) [11]
w ith equivalent quantities of diphenyl(2-hydroxy-
phenyl)phosphine [1 2 ] in dichlorom ethane as a sol-
vent at room tem perature leads to the precipitation
o f virtually quantitative yields of a colourless, m i-
crocrystalline product (1, m.p. 251°C [dec.]). The
com plex can be obtained as single crystals on slow
evaporation of the solvent from saturated solutions
in C H 2CI2. The corresponding brom ide com plex
is obtained sim ilarly using (M e2S)AuBr [13] as
the starting m aterial (2, 92% yield, m.p. 226°C)
(e q .(l)).
In attem pts to further delineate the scope o f this
supram olecular chem istry of gold(I) com plexes, we
have now introduced ortho-hydroxy-functionalized
triphenylphosphine and its trim ethylsilyl ether as
ligands for gold(I) halides. The results show that this
type of ligand is just too bulky to leave enough space
for a close approach of the gold atom s. Thus only
hydrogen bonding rem ains as a m eans of aggrega-
tion, and the silylated derivatives finally appear as
m onom eric m olecules. These studies are an exten-
sion also of recent investigations in the coordination
The pentafluorophenylgold(I) com plex (3) is gen-
erated in the reaction of (CöF5)Au(tetrahydrothio-
phene) [14] with (2 -HO-C6H4)PhbP as shown by
the spectroscopic data of the reaction mixture and
o f the products obtained after standard work-up (eq.
(1)). The spectra indicate that significant am ounts
o f a phosphine oxide are also present, which render
the separation of com plex 3 very difficult, and no
satisfactory purity could be achieved.
Reprint requests to Prof. Dr. H. Schmidbaur.
0932-0776/99/0100-0030 $ 06.00 (c) 1999 Verlag der Zeitschrift für Naturforschung. Tübingen • www.znaturforsch.com
K
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C. Hollatz et al. • DiphenyI(2-hydroxy-phenyl)phosphine
31
OH
OH
CH2C1,
•Me,S/tht
Me2SAuX/
(tht)AuC6F5
PPh,
P -A u -X
Ph2
1 : X = CI
2
3
: X = Br
: X = C6F5
( 1 )
O H .....NEt,
P -A u -C I
Ph,
Ph2
OH ■“ CI • Au - P
P -A u -C I - HO
Ph,
Ph
O - A u - P
+
NEt,HCl
!4
P - A u - 0
Ph2
OH
toluene, 100°C
- CÄHF,
2 )
P-A u-C JF<
Ph,
OSiMe,
OSiMe,
OSiMe,
PPh,
CH2C12
- Me,S/tht
KI/H20/CH2C12
-KCl
Me2SAuX/
(tht)AuC6F5
P -A u -I
Ph,
P -A u -X
Ph,
5
6
8
: X = CI
: X = Br
: X = C6F5
The chloro com plex 1 form s a weak adduct w ith
triethylam ine (4), w hich can be precipitated from a
toluene solution upon addition of pentane. It looses
NEts upon attem pted crystallization. The prim ary
product has been identified by spectroscopic data
w hich suggest a fixation of the am ine via hydrogen
bonding at the phenolic function (eq. (2)). A sim -
ilar type o f adduct form ation has previously been
observed with gold(I) com plexes of phosphinous
acid [15].
The trim ethylsilyl ether of the above ligand, (2-
M e^SiO -C öH ^PhbP [ 1 2 ], undergoes the same set
of reactions w ith (M e2S)A uCl, (M e2S)A uBr or
CöH^AuCtht) to give the corresponding 1:1 com -
plexes in high yields (eq. (3)). The chloro com -
plex 5 can be converted into the iodo com plex 7
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C. Hollatz et al. • Diphenyl(2-hydroxy-phenyl)phosphine
32
C3
Fig. 1. Molecular structure of compound 5 (ORTEP draw-
ing with 50% probability ellipsoids, H-atoms omitted for
clarity). Selected bond lengths [A] and angles [°]: Au-P
2.2294(8), Au-Cl 2.2851(8); P-Au-Cl 177.30(3), Si-O-
C 112 132.8(2).
by treatm ent w ith aqueous potassium iodide. W hile
isolation of the products presents no problem s for
the halide com plexes, the pentafluorophenyl com -
pound 8 is again difficult to purify. A ttem pted ther-
m olysis of 3 to liberate C 6F5H did not lead to the
expected O -A u-P bonded oligom er, but gave com -
plex m ixtures of products.
The results of elem ental analyses and of the
NM R spectroscopic and m ass spectrom etric in-
vestigations confirm ed the proposed stoichiom e-
try and L-A u-X structure. Redistribution of ligands
[16], to give e.g. hom oleptic ionic species [L2A u]+
[AuX2]“ , was not observed for any of the solutions
in chloroform at am bient tem perature. However, in
the FAB m ass spectra this ligand exchange was ob-
served and cations [L2A u]+ could be detected. It
should be noted that in the hom oleptic cation there
is a chance for inter-ligand hydrogen bonding, but
obviously this opportunity is not a sufficient driv-
ing force for the exchange o f ligands. The N M R
chem ical shifts and m ultiplicities were as expected
on the basis of literature data for related neutral
com pounds.
Fig. 2a, b. Molecular structure of the two crystallograph-
ically independent molecules of compound 7 (ORTEP
drawing with 50% probability ellipsoids, H-atoms omit-
ted for clarity). Selected bond lengths [A] and an-
gles [°]: A ul-Pl 2.247(2), A ul-Il 2.5381(9); Pl-A ul-
II 179.52(6), Si 1-01-Cl 12 133.7(6) - Au2-P2 2.252(2),
Au2-I2 2.5677(7); P2-Au2-I2 178.53(6), Si2-02-C212
132.0(5).
The ligand has a propeller-type conform ation dis-
torted by the presence of the ortho-trim ethylsiloxy
substituent at one of the phenyl rings. The C-P-C
and C-P-A u angles at phosphorus are as yet in the
narrow ranges from 104.24(13) to 107.91(13)° and
from 111.41(9) to 114.68(10)°, respectively. The P-
Au-Cl unit is linear [177.30(3)°] w ith standard Au-
P and Au-Cl bond lengths. The distance O • Au
[3.353 A] is too large to suggest coordinative bond-
ing. The Si-O-C angle [132.8(2)°] also indicates a
configuration typical for free silylethers.
Structural Investigations
Crystals of the chloro (5) and iodo (7) com -
plexes are not isom orphous. The lattice of the for-
m er (5, triclinic, space group P i, Z = 2) contains
individual m olecules w ith no sub-van der W aals
contacts (Fig. 1). These m olecules are chiral and
the enantiom ers are related by an inversion center.
Crystals of the iodo analogue 7 are also triclinic
(space group P i, Z = 4), but the lattice contains
two independent m olecules w hich differ in som e
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33
C. Hollatz et al. ■Diphenyl(2-hydroxy-phenyl)phosphine
Fig. 4. Molecular structure of the pairs of molecules
of compound 1 (ORTEP drawing with 50% probabil-
ity ellipsoids, C-H atoms omitted for clarity). Selected
bond lengths [A] and angles [°]: Au-P 2.2226(2), Au-
C1 2.285(2); P-Au-Cl 176.85(8); hydrogen bonding: O-H
1.049, Cl -H 2.040; O-H- • Cl 169.0.
Fig. 3. Superposition of the two crystallographically in-
dependent molecules of compound 7.
details of conform ation (Fig. 2a, b). A superposi-
tion of the two structures (Fig. 3) shows that the
m olecules are alm ost (non-crystallographic) m irror
im ages (two enantiom ers). For each of the indepen-
dent m olecules there is an enantiom er related by
a crystallographic center of inversion. The P-Au-
I units are both linear [179.52(6) and 178.53(6)°
for A ul and Au2, respectively], and there is only
a m inor difference between the tw o Si-O -C angles
[133.7(6) and 132.9(5)°].
The structures of com pounds 5 and 7 show that
there is very efficient steric shielding of the P-Au-
X units w hich prevents any interm olecular contact
betw een gold atom s or betw een gold and halogen
atom s. There is a parallel head-to-tail arrangem ent
of these units in the lattice, but the distances [e.g.
A ul- -Au2 6.163 A] are too large to allow any
direct interaction. It is interesting to note that the
siloxy groups are not accepted by the gold atom s as
auxiliary (intra- or interm olecular) ligands. Clean
tw ofold coordination is m aintained.
Crystals of com plex 1 are m onoclinic (space
group P2)/n, w ith Z = 4), and the lattice contains
pairs of m olecules, the individual units of w hich are
related by sym m etry (Fig. 4). Bond lengths and an-
gles of the C 3P-AU-CI unit in the m onom er are very
sim ilar to those in the silylether 5, but the conform a-
tion of the triphenylphosphine propeller is changed
such that the phenolic groups can m aintain hydro-
gen bonds with the chloro ligand of a neighbour-
ing m olecule. This hydrogen bonding is responsi-
ble for the form ation of dim eric units. The details of
these hydrogen bonds [O-H 1.049 A, Cl
H 2.040
A, O-H-- Cl 169.0°] are consistent with param e-
ters for other hydrogen-bonded contacts of this type
[1 7 -1 9 ],
The oligom erization of com pound 1 in the crystal
is probably responsible for the rather poor solubil-
ity of the com plex in di- or trichlorom ethane and
m ethanol. The solubility is increased upon addi-
tion of triethylam ine owing to the cleavage of the
dim er and form ation of new hydrogen bonds of the
m onom ers w ith NEt^ (eq. (2)). Evidence for the dif-
ferent types of hydrogen bonding is available also
from N M R and IR investigations, although the ef-
fects are not always fully convincing due to solubil-
ity problem s and to the sensitivity of the sam ples to
traces of moisture.
In summary, the present study has shown that
a triphenylphosphine ligand w ith only one ortho-
substituent at one of the phenyl groups is already too
large to allow an intim ate interm olecular m utual ap-
proach of the gold atoms. The metal atom s are also
reluctant to accept the phenolic function as an aux-
iliary donor, and this is also true for the trim ethylsi-
lyl ethers of the title ligand. The com plexes with
this even bulkier substituent are m onom ers w ith a
standard linear tw o-coordinate structure. N o signif-
icant ligand redistributions to give hom oleptic ionic
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34
C. Hollatz et al. ■Diphenyl(2-hydroxy-phenyl)phosphine
153 mg. 92% ; white solid, m.p. 226°C. stable to air
and moisture, sparingly soluble in dichloromethane, chlo-
roform and methanol, and insoluble in diethylether and
pentane. - 'H NMR: b = 7.36-7.71 [m. Ph]; 6.77-7.00
[m. C6H4], - i3C{'H} NMR: b = 157.9 [d, 2j(P,C) = 5.37
Hz, C2-C6H4]; 134.2 [d. 2/(P.C) = 13.81 Hz, C2/6-Ph];
134.1 [s, C6-C6H4]; 133.8 [s, C4-C6H4]; 131.8 [s, C4-
Ph]; 129.1 [d. 3/(P,C) = 12.28 Hz. C3/5-Ph]: 128.3 [d.
'/(P.C) = 62.93 Hz, Cl-Ph]; 121.0 [d. V(P,C) = 10.74
Hz, C5-C6H4]; 116.8 [d. 3/(P.C) = 5.37 Hz, C3-C6H4];
CI-C6H4 was not detected. - ' 1P{ 1H} NMR: b = 25.9 [s],
- MS (FAB): m/z = 1029 [2M - Br]+, 556 [M +1]+, 554
[M - 1]+, 475 [M - Br]+.
isom ers [L2A u]+and [A uX t]- have been observed
by NM R spectroscopy in solution, although mass
spectrom etric studies have indicated that cations
[L tA u]+ are form ed in the vaporization and ion-
ization process. Thus inter-ligand hydrogen bond-
ing (-O H /-O H ) in hom oleptic cations [L2Äu]+ is
also not com peting effectively with the O-H - Cl hy-
drogen bonding observed for the heteroleptic com -
pound 1 as the sole binding contacts between the
m olecules. Sim ilar results have been obtained for
analogous phosphinous acid com plexes [15].
Experimental Section
C i8H,5AuBrOP (555.16)
General: All experiments were routinely carried out in
an atmosphere of dry nitrogen. Solvents were dried and
saturated with nitrogen; glassware was oven-dried and
filled with nitrogen. Standard analytical and spectroscopic
equipment was used throughout. Starting materials were
commercially available or prepared and purified follow-
ing published procedures. All NMR data were recorded
in CDCb at 23°C unless otherwise stated.
Calcd C 38.94 H 2.72 %,
Found C 38.69 H 2.93 %.
Pentafluorophenyl[diphenyI-(2-hydroxy-phenyl)phos-
phine]gold(I) (3): Pentafiuorophenyl(tetrahydrothiophe-
ne)gold(I) (136 mg. 0.3 mmol) and Ph2P(C6H40H) (84
mg, 0.3 mmol) were dissolved in CH2CI2 (20 ml) and the
reaction mixture stirred for 1 h at room temperature. The
solvent was evaporated in a vacuum to leave a volume of
3 ml. Pentane (30 ml) was added to precipitate a white
solid, that contained small amounts of the phosphine ox-
ide Ph2P(0 )(C6H40 H), which could not be separated. -
'H NMR: b = 7.21-7.74 [m. Ph]: 6.76-7.05 [m, C6H4].
- 13C{'H} NMR: b = 157.9 [d, 2/(P,C) = 6.91 Hz, C2-
C6H4]; 148.7 [d, '/(F.C) = 258.60 Hz, C2/6-C6F5]; 141.3
[s br, C4-C6F5]; 137.2 [d, '/(E C ) = 271.67 Hz, C3/5-
C6F5]; 134.4 [s, C6-C6H4]; 134.3 [d, 27(P,C) = 13.82 Hz,
C2/6-Ph]; 134.3 [s, C4-C6H4]; 131.7 [d, 4/(P,C) = 3.07
Hz, C4-Ph]; 129.3 [d,3/(P ,C )= l1.52 Hz, C3/5-Ph]; 128.8
[d, '/(P,C) = 56.79 Hz, Cl-Ph]; 121.4 [d, 3/(P,C) = 8.44
Hz, C5-C6H4]; 117.2 [d, 3/(P,C) = 4.61 Hz, C3-C6H4];
115.0 [d, '/(P.C) = 55.25 Hz. C 1-C6H4). - 31P{1H} NMR:
6 =41.0 [s. Ph2P(0)(C6H40H )]; 31.9 [t,4/(F.P) = 7.40 Hz,
Ph2P(C6H4OH)AuC6F5 3], - l9F{'H} NMR (CF3COOH
as reference): b = -85.8 [t, ’/( F,F) = 20.60 Hz, meta-F];
-83.3 [t, 3/(F,F) = 19.72 Hz, para-F]; -43.1 [d, 3/(F,F) =
14.85 Hz, ortho-F]. - C24H,?AuF5OP (642.31).
/Diphenyl-(2-hydroxy-phenyl)phosphine]gold(I) chlo-
ride (1): (Dimethylsulfide)gold(I) chloride (88 mg, 0.3
mmol) and PhbPtCa^O H) (84 mg. 0.3 mmol) were dis-
solved in CH2CI2 (20 ml) and the reaction mixture stirred
at room temperature. The product precipitated as a white
solid, which was collected by filtration after a reaction
time of 1 h. The solvent of the filtrate was evaporated
in a vacuum to leave a volume of 3 ml. Pentane (30 ml)
was added to precipitate the remainder of the product.
Colourless crystals were obtained by slow evaporation of
a saturated CH2CI2 solution: 150 mg, 98% yield; m.p.
251°C (dec.), stable to air and moisture, sparingly sol-
uble in dichloromethane, chloroform and methanol, and
insoluble in diethylether and pentane. - 'H NMR: b =
7.29-7.68 [m. Ph]; 6.82-7.23 [m, C6H4]; 5.80 [s br, OH],
- 13C {1H} NMR: b = 134.2 [d, 2/(P,C) = 13.82 Hz. C2/6-
Ph]; 134.0 [s, C6-C6H4]; 131.9 [d. V(P,C) = 3.07 Hz,C4-
Ph]; 130.7 [s, C4-C6H4]; 129.2 [d, 3/(P.C) = 12.28 Hz,
C3/5-Ph]; 127.9 [d, ‘/(P,C) = 63.72 Hz, Cl-Ph]; 121.4 [d,
3/(P,C) = 10.75 Hz, C5-Cf,H4]; 117.0 [d, iJ(P,C) = 5.37
Hz, C3-C(,H4]; C I-C 6H4 and C2-C6H4 were not detected.
- 3IP{'H} NMR: b = 22.4 [s], - MS (FAB): ni/z = 753
[{Ph2P(C6H4OH)}2Au]+. 475 [M - Cl]+.
Triethylamine-[diphenyl-(2-hydroxy-phenyl)phosphi-
ne]gold(I) chloride (4): [Diphenyl-(2-hydroxy-phenyl)-
phosphine]gold(I) chloride (1) (51 mg, 0.1 mmol) was
dissolved in toluene (50 ml) and the clear colourless so-
lution was treated with an excess of NEt3 (1 ml). Af-
ter stirring for 1 h at room temperature the solvent was
evaporated in a vacuum to leave a volume of 3 ml. Pen-
tane (40 ml) was added to precipitate a white solid,
that contained small amounts of the phosphine oxide
Ph2P(0 )(C6H40 H). Attempted purification by crystal-
lization led to the formation of compound 1 with the free
hydroxy function. - 'H NMR: b = 7.17-7.67 [m, 10H.
C I8H ,5AuC10P(510.69)
Calcd C 42.33 H 2.96 %,
Found C 42.25 H 3.03 %.
[Diphenyl-(2-hydroxy-phenyl)phosphine]gold(I) bro-
mide (2): The procedure was the same as described for
1. using 102 mg of (dimethylsulfide)gold(I) bromide (0.3
mmol) and 84 mg of Ph2P(C6H4OH) (0.3 mmol); yield
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C. Hollatz et al. • Diphenyl(2-hydroxy-phenyl)phosphine
35
Table I. Crystal data, data collection, and structure refinement for compounds 1, 5, and 7.
7
1
5
Crystal data
Formula
Mr
Crystal system
Space group
a (A)
*(A )
c (A)
a ( ° )
ß (°)
7 0 ,
V (A )
Peak (gem
Z
C |8H n AuC10P
510.69
monoclinic
P2\/n
8.949(1)
10.894(1)
17.388(1)
90
102.70(1)
90
1653.7(4)
2.051
4
C i|H 2^AuC10PSi
582.87
triclinic
C2,H^AuIOPSi
674.32
triclinic
P\
P\
9.823(1)
10.367(1)
12.484(1)
71.85(1)
76.18(1)
67.59(1)
1106.3(2)
1.750
10.273(1)
14.606(1)
17.107(1)
80.75(1)
79.26(1)
71.70(1)
2379.9(3)
1.882
)
4
2
F(000)
968
564
1272
H(MoKa ) (cm-1)
91.52
69.03
76.03
Data collection
T(°C)
-78
+21
-78
Scan mode
hkl Range
lv-9
UJ
to'-26
-11 — 11,0— 14,
0—22
0.64
0—>12,-15— 17,
-19—20
0.62
0— 12,-12— 13,
-15—»-15
0.64
sin(#/A)max (A-1)
Measured reflections
Unique reflections
4096
5296
5296
8345
8345
3979 [Rinl = 0.0651]
3744
7341
Refls. used for refinement
5165
Refinement
Refined parameters
Final R values [I > 2a(\)]
R l [al
469
199
235
0.0421
0.0951
0.0199
0.0485
0.0403
0.0982
H'/?2|bl
(shift/error)max
Pfin(max/min) (eA-3 )
< 0.001
1.247/ -1.444
< 0.001
1.736/-2.611
< 0.001
0.797/-1.473
[a| R = KIIFol - IFcll / IlFol; [b! wR2 = {[Iw (F02 - Fc2)2] / I[w (F02)2]}1/2; w- = l/[cr(F02) + (ap)2 + bp]: p = (Fa2 +
2Fc2)/3; a = 0.0399 (1), 0.0287 (5), 0.0503 (7); b = 14.32 (1), 1.22 (5), 7.67 (7).
Ph]; 6.53-6.70 [m, 4H, C6H4]; 3.05 [q, 6H, V(H,H) =
7.10 Hz, CH2]; 1.25 [t, 9H, V(H,H) = 7.10 Hz, CH3].
- 3IP{'H} NMR: 6 = 41.0 [s, Ph2P(0 )(C6H40 H)]; 24.0
[s, Ph2P(C6H4OH- •-NEt3)AuCl 4], - MS (FAB): m/z =
612 [M +1]+, 611 [M]+, 610 [M - 1]+, 102 [NEt3 +1]+. -
C24H30AuC1NOP(61 1.90).
solvent from solutions in CH2C12 (157 mg, 90% yield;
m. p. 204°C (dec. > 250°C), stable to air and moisture,
soluble in dichloromethane, chloroform and tetrahydro-
furan, and insoluble in diethylether and pentane). - 'H
NMR: 6 = 7.41-7.68 [m, Ph]; 6.62-6.94 [m, C6H4]; 0.14
[s, Me], - l3C{'H} NMR: 6 = 157.4 [s, C2-C6H4]; 134.2
[d, 2y(P,C) = 13.82 Hz, C2/6-Ph]; 133.9 [s, C6-C6H4];
133.5 [s, C4-C6H4]; 131.6 [d, 4/(P,C) = 2.30 Hz, C4-
Ph]; 129.0 [d, V(P,C) = 12.28 Hz, C3/5-Ph]; 128.6 [d,
'7(P,C) = 63.70 Hz, Cl-Ph]; 121.1 [d, V(P,C) = 9.98
Hz, C5-C6H4]; 118.8 [d, 'i(P,C) = 66.00 Hz, C1-C6H4];
117.7 [d, 3/(P,C) = 5.37 Hz, C3-C6H4]; 0.3 [s, Me], -
3,P{1H} NMR: 6 = 25.8 [s], - MS (FAB): m/z = 897
[{Ph2P(C6H4OSiMe3)}2Au]+, 547 [M - Cl]+, 475 [M -
Cl - SiMe3 +1 ]+.
[Diphenyl-(2-trimethylsiloxyphenyl)phosphine]-
gold(I) chloride (5): (Dimethylsulfide)gold(I) chloride
(88 mg, 0.3 mmol) and diphenyl-(2-trimethylsiloxy-
phenyl)phosphine (105 mg, 0.3 mmol) were dissolved in
CH2C12 (20 ml) and the reaction mixture was stirred for
1 h at room temperature. The solvent was evaporated in a
vacuum to leave a volume of 3 ml. Pentane (30 ml) was
added to precipitate the product as a white solid. Colour-
less crystals were obtained by slow evaporation of the
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C. Hollatz et al. • Diphenyl(2-hydroxy-phenyl)phosphine
CSiH^AuClOPSi (582.87)
Calcd C 43.27 H 3.98 %,
Found C 43.27 H 3.75 %.
that contained small amounts of the phosphine oxide
Ph2P(0 )(C6H40H). Purification of 8 by crystallization
was not successful. - 'H NMR: 6 = 7.31-7.74 [m, Ph];
6.61-6.96 [m, C6H4]; 0.11 [s, Me], - 13C{'H} NMR: 6 =
157.4 [d, 27(P,C) = 6.14 Hz, C2-C6H4]; 134.5 [d, 2J(P,C) =
13.82 Hz. C2/6-Ph]; 134.3 [s, C6-C6H4]; 133.1 [s, C4-
C6H4]; 131.4 [d, 47(P,C) = 2.31 Hz, C4-Ph]; 129.0 [d,
V(P,C) = 11.51 Hz, C3/5-Ph]; 121.1 [d, V(P,C) = 9.21
Hz, C5-C6H4]; 117.5 [d, V(P,C) = 4.61 Hz, C3-C6H4];
0.0 [s, Me]; C 1-Ph, C 1-C6H4 and CöFs were not detected.
- 31P{'H} NMR: 6 = 41.0 [s, Ph2P(0)(C6H40H)]; 36.5
[t, 47(P,F) = 7.04 Hz, Ph2P(C6H4OSiMe3)AuC6F5, 8], -
MS (FAB): m/z =1261 [2M - C6F5]+, 715 [M +1]+, 714
[M]+, 547 [M - C6F5]+, 475 [M - SiMe3 - C6F5 +1], 350
[M - AuC6F5]+. - C27H23AuF5OPSi (714.49).
[Diphenyl-(2-trimethylsiloxyphenyl)phosphine]-
gold(I) bromide (6): The procedure was the same as de-
scribed for 5, using 102 mg of (dimethylsulfide)gold(I)
bromide (0.3 mmol) and 105 mg of the ligand (0.3 mmol);
yield 147 mg, 78% ; white solid, m.p. 158°C, stable to
air and moisture, soluble in dichloromethane, chloroform
and tetrahydrofuran, and insoluble in diethylether and
pentane. - 'H NMR: 6 = 7.39-7.68 [m, Ph]; 6.68-7.00 [m,
C6H4]; 0.14 [s, Me]. - 31P{'H} NMR: Ö= 28.2 [s], - MS
(FAB): m/z = 1174 [2M - Br]+, 628 [M +1]+, 547 [M -
Br]+, 350 [M - AuBr]+.
C2,H23AuBrOPSi + 1/2 Q H ,2 (627.34 + 36.07)
Calcd C 42.55 H 4.41% ,
Crystal structure determinations. Specimens of suit-
able quality and size of compounds 1, 5, and 7 were
mounted in glass capillaries and used for measurements
of precise cell constants and intensity data collection on
an Enraf Nonius CAD4 diffractometer (Mo-A,Q radia-
tion, A(Mo-^Q) = 0.71073 A). During data collection,
three standard reflections were measured periodically as
a general check of crystal and instrument stability. No
significant changes were observed. Lp correction was ap-
plied and intensity data were corrected for absorption ef-
fects (DIFABS). The structures were solved by Patterson
methods (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 idealized
calculated positions and allowed to ride on their corre-
sponding carbon atoms with fixed isotropic contributions
(Uiso(fix) = 1.5 x Ueqof the attached C atom). The O-H atom
of compound 1 was located and included in the refinement
with fixed isotropic contributions (UjS0(fix) = 1.5 x Ueq of
the attached O atom). Further information on crystal data,
data collection and structure refinement are summarized
in Table I. Important interatomic distances and angles are
shown in the corresponding Figure Captions. Anisotropic
thermal parameters, tables of distances and angles, and
atomic coordinates have been deposited with Fachin-
formationszentrum Karslruhe, Gesellschaft für wissen-
schaftlich-technische Information mbH. D-76344 Eg-
genstein-Leopoldshafen. The data are available on re-
quest on quoting CSD No. 410462 (1), 410463 (5), and
410461 (7).
Found C 43.39 H 4 .ll %.
[Diphenyl-(2-trimethylsiloxyphenyl)phosphine]-
gold(l) iodide (7): [Diphenyl-(2-trimethylsiloxyphenyl)-
phosphine]gold(I) chloride 5 (117 mg, 0.2 mmol) was
dissolved in CH2C12 (20 ml) and treated with an excess
of an aqueous solution of KI (10 ml). After stirring for
1 h at room temperature the CH2C12 phase was collected.
The solvent was evaporated in a vacuum to leave a vol-
ume of 3 ml. Pentane (30 ml) was added to precipitate
the product as a white solid. Colourless crystals were ob-
tained by slow evaporation of a CH2C12 solution; 69 mg,
51% yield; m. p. 153°C, stable to air and moisture, solu-
ble in dichloromethane, chloroform and tetrahydrofuran,
and insoluble in diethylether and pentane. - 'H NMR:
6 = 7.43 - 7.71 [m, Ph]; 6.73-6.99 [m, C6H4]; 0.14 [s,
Me], - 31P{'H} NMR: 6 = 32.7 [s], - MS (FAB): m/z =
1221 [2M - 1]+, 675 [M +l]+, 674 [M]+, 547 [M - 1]+, 350
[M - Aul]+.
C2iH23AuIOPSi (674.32)
Calcd C 37.40 H 3.44 %,
Found C 40.64 H 3.75 %.
Pentafluorophenylfdiphenyl-(2-trimethylsiloxyphe-
nyl)phosphine]gold(I) (8): Pentafluorophenyl(tetrahydro-
thiophene)gold(I) (136 mg, 0.3 mmol) and diphenyl-
(2-trimethylsiloxyphenyl)phosphine (105 mg, 0.3 mmol)
were dissolved in CH2C12 (20 ml) and the reaction mix-
ture was stirred for 1 h at room temperature. The solvent
was evaporated in a vacuum to leave a volume of 3 ml.
Pentane (30 ml) was added to precipitate a white solid.
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37
[12] a) T. B. Rauchfuss, Inorg. Chem. 16, 2966 (1977);
C. Hollatz et al. ■Diphenyl(2-hydroxy-phenyl)phosphine
[1] H. Schmidbaur, Gold Bulletin 23, 11 (1990).
[2] H. Schmidbaur, Interdiscipl. Sei. Rev. 17, 213
(1992).
[3] H. Schmidbaur, Chem. Soc. Rev. 397 (1996).
[4] W. Schneider, A. Bauer, H. Schmidbaur,
Organometallics 15, 5445 (1996).
[5] D. M. P. Mingos, J. Yau, S. Menzer, D. J. Williams,
J. Chem. Soc., Dalton Trans. 319 (1995).
[6] J. Vicente, M.-T. Chicote, M. D. Abrisqueta, R.
Guerrero, P. G. Jones, Angew. Chem., Int. Ed. Engl.
36,1203(1997).
b) O. Herd, A. Heßler, M. Hingst, M. Trepper,
O. Stelzer, J. Organomet. Chem. 522, 69 (1996).
[13] G. E. Coates, C. Parkin, J. Chem. Soc. 421 (1963).
[14] a) R. Usön, A. Laguna, J. Vicente, J. Chem. Soc.,
Chem. Commun. 353 (1976); b) R. Usön, A. La-
guna, J. Vicente, J. Organomet. Chem. 131, 471
(1977); c) R. Usön, A. Laguna, J. Vicente, J.
Garcia, B. Bergareche, J. Organomet. Chem. 173,
349 (1979).
[15] H. Schmidbaur, A. M. M. Aly, Angew. Chem., Int.
Ed. Engl. 19, 71 (1980).
[16] A. Bauer, H. Schmidbaur, J. Am. Chem. Soc. 118,
5324(1996).
[17] M. Canestrari, B. Chaudret, F. Dahan, Yong-Sheng
Huang, R. Poilblanc, Tag-Chong Kim, M. Sanchez,
J. Chem. Soc., Dalton Trans. 1179 (1990).
[18] L. Dahlenburg, K. Herbst, M. Kühnlein, Z. Anorg.
Allg. Chem. 623, 250(1997).
[7] C. Hollatz, A. Schier, H. Schmidbaur, J. Am. Chem.
Soc. 119, 8115 (1997).
[8] C. Hollatz, A. Schier, H. Schmidbaur, Inorg. Chem.
Commun. 1, 115 (1998).
[9] C. Hollatz, A. Schier, H. Schmidbaur, J. Chem. Soc.,
Dalton Trans., submitted.
[10] D. Weiß, A. Schier, H. Schmidbaur, Z. Naturforsch.
53b, 1307(1998).
[11] K. C. Dash, H. Schmidbaur, Chem. Ber. 106, 1221
[19] S. B. Sembiring, S. B. Colbran, R. Bishop, D. C.
Craig, A. D. Rae, Inorg. Chim. Acta 228,109 (1995).
(1973).
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