Dibenzotropylidene phosphanes (TROPPs): Synthesis and coinage metal complexes

Article abstract of DOI:10.1039/a801003j

Dibenzocycloheptatrienyl phosphanes (dibenzotropylidene phosphanes = TROPP^R) 11a-c may be easily prepared from dibenzocycloheptatrienyl chloride 8 and the secondary phosphanes R₂PH [9a: R = Ph; 9b: R = 4-Me-C₆H₄; 9c: R = cyclohexyl (Cyc)] in good yields. Alternatively, the di(tert-butyl)phosphanyl substituted TROPP^But derivative 4 was obtained along with the phosphane 5 by a mechanistically still unknown rearrangement of a strained phosphorus ylide I. The conformations of these new phosphanes were established by X-ray analyses performed for the compounds TROPP^But 4 and TROPP^Ph 11a. The R₂P moiety is bonded to an axial position of the central seven-membered ring, which adopts a boat conformation. Thereby a rigid concave binding site containing a phosphane and an olefin function is formed, which should allow the synthesis of a wide range of transition metal complexes. In order to test how far the particular shape of the TROPP-type ligands enforces metal-olefin interactions, the coinage metal complexes [(TROPP^Ph)Cu(μ₂-Cl)]₂, 13, [(TROPP^Ph)Ag(μ₂-O₂SOCF₃)] ₂, 16, [(TROPP^Ph)₂Ag][O₃SCF₃], 17 and [(TROPP^Ph)AuCl], 19 were prepared. These were completely characterized by multinuclear NMR experiments in solution and the solid state, as well as by X-ray analyses. The structural and NMR data show that the interaction between the metal center M and the olefin moiety of the TROPP ligand is weak and decreases in the order Cu > Ag > Au. Indeed, for 19 (M = Au) no interaction could be observed. In the silver complex 17, coupling between an Ag nucleus and a proton of a bonded olefin was determined for the first time [J(^109/107Ag,¹H) = 0.4 Hz]. In solution the complexes derived from TROPP-type ligands seem to have an enhanced (kinetic) stability.

Full text of DOI:10.1039/a801003j

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Dibenzotropylidene phosphanes (TROPPs): synthesis and coinage
metal complexes¤
Jorg Thomaier,a Souad Boulmaaz,a Hartmut Schonberg,a Heinz Ruegger,a Antonio Currao,a
Hansjorg Grutzmacher,*,a Harald Hillebrechtb and Hans Pritzkowc
a ET H Zurich, L aboratorium f ur Anorganische Chemie, Universitatsstrasse 6, CH-8092 Zurich,
Switzerland
b Institut f ur Anorganische Chemie der Universitat, Albertstrasse 21, D-79104 Freiburg, Germany
c Anorganische Chemisches Institut der Universitat, Im Neunheimer Feld 270, D-69140
Heidelberg, Germany
Dibenzocycloheptatrienyl phosphanes (dibenzotropylidene phosphanes \ TROPPR) 11aÈc may be easily
prepared from dibenzocycloheptatrienyl chloride 8 and the secondary phosphanes R PH [9a: R \ Ph; 9b:
2
R \ 4-Me-C H ; 9c: R \ cyclohexyl (Cyc)] in good yields. Alternatively, the di(tert-butyl)phosphanyl
6
4
substituted TROPPBut derivative 4 was obtained along with the phosphane 5 by a mechanistically still unknown
rearrangement of a strained phosphorus ylide I. The conformations of these new phosphanes were established
by X-ray analyses performed for the compounds TROPPBut 4 and TROPPPh 11a. The R P moiety is bonded to
2
an axial position of the central seven-membered ring, which adopts a boat conformation. Thereby a rigid
concave binding site containing a phosphane and an oleÐn function is formed, which should allow the synthesis
of a wide range of transition metal complexes. In order to test how far the particular shape of the TROPP-type
ligands enforces metalÈoleÐn interactions, the coinage metal complexes [(TROPPPh)Cu(l -Cl)] , 13,
2
2
[(TROPPPh)Ag(l -O SOCF )] , 16, [(TROPPPh) Ag][O SCF ], 17 and [(TROPPPh)AuCl], 19 were prepared.
2
2
3 2
2
3
3
These were completely characterized by multinuclear NMR experiments in solution and the solid state, as well
as by X-ray analyses. The structural and NMR data show that the interaction between the metal center M and
the oleÐn moiety of the TROPP ligand is weak and decreases in the order Cu [ Ag [ Au. Indeed, for 19
(M \ Au) no interaction could be observed. In the silver complex 17, coupling between an Ag nucleus and a
proton of a bonded oleÐn was determined for the Ðrst time [J(109@107Ag,1H) \ 0.4 Hz]. In solution the
complexes derived from TROPP-type ligands seem to have an enhanced (kinetic) stability.
Recently we reported the synthesis of a stable monomeric
paramagnetic d9-rhodium(0) complex using the novel
(dibenzo[a,d]cyclohepten-5-yl)diphenyl phosphane (tropyl-
idenyldiphenyl phosphane) (11a; Scheme 2 vide infra) as the
ligand.1 In this article, we report on the synthesis of dibenzo-
tropylidene type phosphanes and their complexation behavior
towards the coinage metal ions Cu`, Ag` and Au`. Pre-
viously, Herberhold et al. reported the synthesis of the
tris(tropylidenyl)phosphane 12 and the Ðrst examples of coor-
dination compounds thereof, such as 2.3 Independently, and
by accident, we found an access to derivatives of this phos-
phane, namely dibenzotropylidenyl(bistert-butyl)phosphane 4,
in an attempt to prepare the strained phosphorus ylide I from
the tricyclic phosphonium salt 34 (Scheme 1). We will name
these phosphanes TROPPR, where the superscript R indicates
the substituent bonded to phosphorus, for example 4 \
TROPPBut.
The particular shape of TROPP-type ligands and their elec-
tronic characteristics make these phosphanes promising
ligands in transition metal chemistry for the following reasons.
(i) The phosphorus center and the CxC double bond of the
cycloheptenyl ring in TROPPs form a stereochemically well-
deÐned concave pocket in which a wide range of transition
metals may be hosted.
(iii) The dibenzotropylidene moiety adopts a rather rigid
boat conformation with a high energy barrier for intercon-
version. This has been thoroughly investigated by means of
dynamic NMR spectroscopy for a wide range of substituted
cycloheptatrienes.5 For TROPPs interconversion barriers
higher than 120 kJ mol~1 may be assumed.
(iv) In a Ðrst approximation, the phosphorus center serves
as a r-donor ligand while the oleÐnic moiety acts as a p
acceptor. This allows the synthesis of complexes with the
metal centers in unusual oxidation states like Rh0 or Rh~I.1
(v) Amino-substituted dibenzotropylidenes are very efficient
But
But
Cl–
A
P+ CH2
P
H
H
P
B
Rh
C
Cl
1
2
3
NaN(SiMe3)2
–NaCl
–HN(SiME3)2
But
CH2
H
ButP
But
H
H
P
(ii) The bulky R P groups are expected to bind always in
the sterically preferred endo position of the dibenzotropylidene
H
PBut2
2
+
ring.
I
5
4
¤ Dedicated to Professor Gottfried Huttner on the occasion of his
60th birthday.
Scheme 1
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almost quantitatively in a 40:60 ratio. It is likely that the
phosphorus ylide I has originally been formed and subse-
quently underwent a complex rearrangement. The mechanism
of this reaction is still unclear and under current investigation.
We performed single crystal X-ray analyses of the products 4
and 5 and the results are shown in Fig. 1 and 2, respectively.
Selected bond lengths and angles of 4 and 5 are given in
Tables 1 and 2, respectively.
The dibenzocycloheptatrienyl moieties in 4 and 5 adopt
boat conformations. In 4 the But P group is bonded to the
2
carbon center at the bow of the boat in an endo position with
respect to the carbonÈcarbon double bond at the stern. All
PwC bonds are relatively long [average: 1.911(4) A] due to
the steric encumbrance of the phosphorus center. The sum of
bond angles at the phosphorus center [&(P) \ 313.2¡] is like-
Fig. 1 Molecular structure of 4. Selected bond lengths and angles
are given in Table 1
anti-depressive agents (for example isopavine) and hence the
chemistry of benzotropolones is rather well developed.6 This
will allow the facile synthesis of a wide range of di†erent
TROPPs.
(vi) Di†erently substituted chiral tropolones (which serve as
starting materials in Scheme 3, vide infra) are natural
products7 and may be taken as a chiral pool for the synthesis
of TROPP enantiomers when required. Moreover, intro-
ducing one substituent either in one-half of the hydrocarbon
part or at the phosphorus center will break the C symmety of
s
TROPPs like 4 and lead to chiral ligands.
Dibenzotropylidenyl phosphanes (TROPPs) have some
advantages over the tris(cycloheptatrienyl)phosphane 1, inves-
tigated by Herberhold et al. The latter is sterically much more
Ñexible. By X-ray analysis and temperature dependent NMR
spectroscopy, the axial (ring C in 1, see Scheme 1) as well as
the equatorial binding modes (rings A and B in 1) of the phos-
phanyl group have been veriÐed. Furthermore, the presence of
nine (!) oleÐnic units per phosphorus center in 1 shall lead to a
diversiÐed and rich but less well-deÐned coordination chem-
istry.8 In TROPPs, however, the phosphorus center and the
single oleÐnc unit shall serve as preferred binding sites,
making the coordination chemistry more predictable. Further-
more, the benzo groups attached to the seven-membered ring
lead to funnel-shaped coordination environments around the
metal center, facilitating low coordination numbers. In
summary, the dibenzotropylidene moiety forming a rigid
concave binding site may be regarded as a versatile “platformÏ,
which will allow the investigation of the reactivity of metal
centers in electronically very di†erent but well-deÐned
environments.
Fig. 2 Molecular structure of 5. Selected bond lengths and angles
are given in Table 2
Table 1 Selected bond lengths (A) and angles (¡) of 4
PwC20
PwC1
1.905(4)
1.913(3)
1.914(4)
1.514(4)
1.521(4)
C4wC5
C4wC3
C5wC6
C7wC6
C2wC3
1.327(5)
1.465(5)
1.467(5)
1.401(5)
1.401(5)
PwC16
C1wC7
C1wC2
C20wPwC1
C20wPwC16
C1wPwP
102.5(2)
109.2(2)
101.5(2)
108.2(3)
115.1(2)
C2wC1wP
C5wC4wC3
C6wC7wC1
C7wC6wC5
C3wC2wC1
112.4(2)
127.7(3)
122.2(3)
123.6(3)
121.9(3)
C7wC1wC2
C7wC1wP
Does the form of TROPP-type ligands enforce a metalÈ
oleÐn interaction? To answer this question, we prepared some
TROPP complexes of transition metals that form rather
stable phosphane complexes but notoriously weak oleÐn com-
plexes. Therefore, complexes of 11a and metal ions of the
coinage metals Cu, Ag, and Au were prepared.9
Table 2 Selected bond lengths (A)and angles (¡) of 5
P1wC4
P1wC16
P1wC20
C1wC2
C1wC7
1.855(2)
1.890(2)
1.895(2)
1.502(3)
1.505(3)
C2wC3
C3wC4
C4wC5
C5wC6
C6wC7
1.408(3)
1.495(2)
1.348(2)
1.475(2)
1.403(2)
Results and Discussion
C4wP1wC16
C4wP1wC20
C16wP1wC20
C2wC1wC7
C3wC2wC1
C2wC3wC4
C5wC4wC3
100.39(8)
107.00(8)
111.79(8)
109.9(2)
120.1(2)
122.0(2)
122.6(2)
C5wC4wP1
C3wC4wP1
C4wC5wC6
C4wC5wH5
C6wC5wH5
C7wC6wC5
C6wC7wC1
122.86(12)
114.52(12)
128.8(2)
117.4(10)
113.7(10)
121.8(2)
Syntheses
Synthesis of TROPP-type ligands. Preparation of TROPPBut
4. As mentioned above, 4 was Ðrst obtained in an attempt to
prepare the ylide I as shown in Scheme 1. However, in the
course of this reaction the phosphanes 4 and 5 were obtained
118.9(2)
948
New J. Chem., 1998, Pages 947È958

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wise large. As might be expected, there is a considerable bond
length alternation within the seven-membered ring. The
C4xC5 bond is rather short [1.327(5) A] while the bonds
C4wC3 and C5wC6 to the benzo groups are 1.466(5) A long.
The distances of the C2(7)xC3(6) bonds [1.401(5) A] belong-
ing to the annulated benzo groups, as well as to the tropyli-
dene ring, are typical for conjugated arene CxC bonds. The
remaining two [C1wC2(7)] bonds connecting the arene ring
with the bow-carbon center of the seven-membered ring
[1.514(4), 1.521(4) A] correspond to CwC single bonds. These
structural features are found in the structures of all com-
pounds discussed in this work. Based on these structural data
it may be concluded that the CxC double bond in the tropy-
lidene ring is only weakly conjugated with the benzo groups.
In accordance with this assumption, the 13C NMR data of the
C2 and C3 carbon centers (132.7 ppm) do not di†er signiÐ-
cantly from the values found for 1 or tropylidene, C C , itself
7 8
(131.2 ppm). The structural features of the seven-membered
carbon cycle in 5 resemble closely the ones observed in 4,
showing the expected bond length alternation, although it is
slightly less pronounced compared to 4. Noteworthy is the
length of the C4xC5 double bond [1.348(2) A] and the sum
of bond angles at the phosphorus center (319.2¡). Because of
Fig. 3 Molecular structure of 11a. Selected bond lengths and angles
are given in Table 3
the But P group, the 13C NMR resonances of the carbon
2
mixtures in which the components interconvert on the NMR
timescale, as indicated by the exchange-broadened 1H NMR
resonances at 298 K, while the phosphanes 11aÈc are obtained
exclusively in the form of one isomer. In the solid state, this
was shown to be the endo isomer by X-ray analysis of of
TROPPPh, 11a (Fig. 3), and we assume it maintains the same
conformation in solution. Selected bond lengths and angles
for 11a are given in Table 3.
centers forming the double bond are both shifted to higher
frequency (ca. 140 ppm) in comparison to 4.
Preparation of TROPPPh, 11a, TROPPTol, 11b and
TROPPCyc, 11c. In a continuation of our work, we searched
for a more convenient access to dibenzotroplylidenylphosph-
anes. Indeed, the synthesis of these ligands is fairly simple
and depicted in Scheme 2.
As in TROPPBut, 4, the phosphanyl group in TROPPPh is
bonded in the axial position of the cycloheptatrienyl ring. The
lone pair of electrons at the phosphorus center points towards
the CxC double bond. Apart from the smaller sum of bond
angles at the phosphorus center (304.3¡), which reÑects the
diminished steric congestion, the molecular shapes of 11a and
4 are identical within the experimental errors. Hence very
similar structures are also inferred for the TROPPTol, 11b
(Tol \ 4-MeC H ), and TROPPCyc, 11c (Cyc \ cyclohexyl),
Dibenzotropolone 6 is quantitatively reduced by sodium
tetrahydroborate in methanol to give dibenzotropolol 7,
which was used after drying under vacuum without further
puriÐcation. Subsequently 7 is transformed into the corre-
sponding chloride 8 using thionyl chloride. When a toluene
solution of cycloheptenyl chloride 8 is slowly added to a solu-
tion of a secondary phosphane R PH, 9aÈc, at ambient tem-
2
perature, a white precipitate of the hydrophosphonium salt,
6
4
10aÈc, is formed. At elevated temperature hydrochloride is
eliminated and the desired phosphanes 11aÈc are obtained in
good yields (70È85%) after recrystallization from acetonitrile.
It is advantageous to add the chloride 8 to a solution of phos-
phane 9 and to perform the reaction in non-polar solvents
from which the hydrophosphonium salts precipitate in order
to surpress the formation of bis(tropylidenyl)phosphonium
salts, which are undesired side products.2 It is noteworthy that
solutions of the alcohol 7 and chloride 8 contain exo/endo
derivatives. This is further supported by the NMR spectra,
which are quite similiar for all TROPPR-type ligands, 4 and
11aÈc. In the 1H NMR spectra, the resonance signal due to
the benzylic hydrogen center bonded adjacent to the phos-
phorus is observed between 4.50È4.93 ppm [2J(31P1H) \ 3.4È
6.1 Hz]. The oleÐnic hydrogen centers of the seven-membered
ring are observed in the range of 6.76È6.99 ppm and the 13C
NMR resonances of the corresponding carbon nuclei are
found at 132.7 ^ 1 ppm for all TROPP-type ligands prepared
so far.
OH
Cl
O
H
H
Synthesis of TROPP-coinage metal complexes. The synthe-
sis of the CuI, AgI and AuI complexes is summarized in
Scheme 3.
NaBH4
MeOH
SOCl2
8
6
7
Table 3 Selected bond lengths (A) and angles (¡) of 11a
+
R2P
R2PH
P1wC22
P1wC16
P1wC1
C1wC7
C1wC2
1.827(3)
1.837(3)
1.907(3)
1.505(4)
1.507(4)
C2wC3
C3wC4
C4wC5
C5wC6
C6wC7
1.409(4)
1.447(4)
1.328(4)
1.456(4)
1.406(4)
H
H
Cl–
R2PH 9a-c
C22wP1wC16
C22wP1wC1
C16wP1wC1
C7wC1wC2
C7wC1wP1
C2wC1wP1
103.22(12)
99.58(12)
101.50(12)
115.0(2)
109.5(2)
111.4(2)
C3wC2wC1
C2wC3wC4
C5wC4wC3
C4wC5wC6
C6wC7wC1
122.4(3)
123.7(3)
129.1(3)
128.9(3)
122.6(2)
11a-c
10a-c
a
b
c
C6H5 4-MeC6H4 c-C6H11
R
Scheme 2
New J. Chem., 1998, Pages 947È958
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Cl
PPh2
Cu
Ph2P
Cu
+ 2/n[Cu(PPh2)]n
2
12
Cl
Cl
8
13
2 CuCl
14
R2P
PPh2
Ag
2
O
O
CF3
2 AgOSO2CF3
Ag
15
SO O
P
Ph2
11a
SO
F3C
O
16
+11a
Fig. 4 Molecular structure of 13. Selected bond lengths and angles
are given in Table 4
Ph2
P
Ph2
P
(Ph3P)AuCl
18
tetrahedral coordination site formed by the phosphorus and
the two chlorine centers as well as by the midpoint of the
CxC double bond of the ligand. The copper centers do not
bind symmetrically to the oleÐnic carbon atoms C4 and C5
and thus the CuwC distances vary from 2.366(4) A to 2.453(4)
A [average: 2.413(4) A]. These distances are considerably
longer than the CuwC bond lengths in [Cu (l -Cl) (COD) ]
11a
Ag
Au
Cl
–Ph3P
P
Ph2
19
17
Scheme 3
2
2
2
2
In order to prepare the copper complex 13, we reacted in
THF the chloride 8 with one equivalent of the polymeric
copper diphenylphosphide 12, which can be prepared easily
from diphenylphosphane, 9a, and copper tert-butoxide,
[CuOBut] .10 After recrystallization from acetonitrile,
complex 13 is obtained in the form of yellow crystals in about
60% yield. By this reaction we found a third convenient access
to TROPP-type ligands. Recently, we reported the intro-
duction of phosphido groups into organic halides by copper
reagents, which proved to be a simple method for the synthe-
sis of polyfunctional phosphanes.11 Remarkably, neither the
reaction of 8 with lithium diphenylphosphide, LiPPh , nor
reactions using the dibenzotropylium salt (C
and 12 or LiPPh gave 11a in acceptable yields. Instead,
complex reaction mixtures were obtained. The ligand is easily
(2.05È2.22 A) containing a planar Cu Cl ring.13 The C4xC5
2
2
distances in 13 [average: 1.353(5) A] are only slightly longer
than in the free ligand 11a [1.328(4) A] but are much shorter
than the complexed CxC bond in [Cu (l -Cl) (COD) ] (1.41
2
2
2
2
A).14 The CuwP distances [average: 2.216(2) A] and the
CuwCl distances [average: 2.348(2) A] lie in the range
expected for CuI compounds.13 The rather long PwC bond
between the phosphorus center and the carbon atom of the
seven-membered ring in 11a [1.907(3) A] becomes a little
shorter upon complexation of the phosphorus center in 13
[1.874(4) A]. The sum of CwPwC bond angles in 13 is slight-
ly increased by 7.4¡ [&(P) \ 311.8¡]. The only signiÐcant
structural indication for a copperÈoleÐn interaction is thus the
deviation from planarity of the copper center from its P,Cl,Cl
coordination sphere. Assuming the absence of a copperÈoleÐn
interaction, trigonal planar coordination by the phosphorus
and two chlorine centers is expected, which as a result would
give 360¡ as the sum of the two PwCuwCl and the Clw
CuwCl angles. In 13, these sums of bond angles amount to
344.9¡ and 343.7¡ at Cu1A and Cu1B, respectively, which can
4
2
H
`) [BF ~]
15 11
4
2
liberated from complex 13 by adding a dilute aqueous cyanide
solution and extracting the phosphane with an organic
solvent. Alternatively, the copper complex 13 can be clas-
sically prepared from copper(I) chloride, 14, and the ligand
11a in acetonitrile. After recrystallization 13 is obtained in
about 70% yield.
Adding a toluene solution of 11a to a toluene solution of
silver triÑate (silver triÑuoromethanesulfonate), 15, leads to the
mono-TROPPPh silver complex 16. Silver triÑate is known to
form rather stable oleÐn complexes when compared to silver
salts containing other anions.12 Upon addition of a second
equivalent of 11a to 16 (or by mixing 15 with two equivalents
of 11a) the bis-TROPPPh silver complex 17 is quantitatively
obtained. Both silver complexes form colorless, light-sensitive
crystals.
Table 4 Selected bond lengths (A) and angles (¡) of 13
Cu1AwP1A
Cu1AwCl1A
Cu1AwCl1B
Cu1AwC5A
Cu1AwC4A
Cu1AwCu1B
Cu1BwP1B
Cu1BwCl1B
Cu1BwCl1A
Cu1BwC5B
Cu1BwC4B
P1AwC1A
2.213(2)
C2AwC3A
1.407(5)
1.462(5)
1.351(5)
1.468(5)
1.408(5)
1.879(4)
1.511(5)
1.512(5)
1.403(5)
1.468(6)
1.355(5)
1.468(5)
1.411(5)
2.3397(13) C3AwC4A
2.347(2)
2.408(4)
2.453(4)
2.832(2)
C4AwC5A
C5AwC6A
C6AwC7A
P1BwC1B
2.2180(14) C1BwC2B
Finally, the gold complex 19 was prepared by a simple
2.3426(13) C1BwC7B
ligand-displacement reaction from (Ph P)AuCl, 18, and 11a.
2.362(2)
2.366(4)
2.425(4)
1.869(4)
1.510(5)
1.513(5)
C2BwC3B
C3BwC4B
C4BwC5B
C5BwC6B
C6BwC7B
3
The TROPPPh gold complex 19 is obtained in the form of
colorless, air-stable crystals in 83% isolated yield.
X-ray crystallography: molecular structures
C1AwC2A
C1AwC7A
[Cu (l -Cl) (TROPPPh) ], 13. The copper compound 13
2
2
2
2
exists in the solid state in the form of l -chloride-bridged di-
P1AwCu1AwCl1A 121.31(5)
P1AwCu1AwCl1B 125.12(6)
Cl1AwCu1AwCl1B 98.46(6)
P1BwCu1BwCl1A
125.59(5)
2
nuclear complexes, clathrated with four molecules of acetoni-
Cl1BwCu1BwCl1A 97.95(5)
P1BwCu1BwC5B
Cl1BwCu1BwC5B
P1BwCu1BwC4B
Cl1BwCu1BwC4B
95.50(10)
122.73(10)
92.98(11)
97.41(10)
trile, separated by normal van der Waals distances. A
SCHAKAL view of the complex is given in Fig. 4, selected
bond lengths and angles of 13 are given in Table 4.
P1AwCu1AwC5A
94.47(10)
Cl1BwCu1AwC5A 89.37(10)
P1AwCu1AwC4A 93.53(10)
The central four-membered Cu Cl cycle is folded by 45.7¡,
Cl1AwCu1AwC4A 101.40(10) Cu1AwCl1AwCu1B 74.10(5)
2
2
allowing a rather short copperÈcopper distance of 2.832(2) A.
P1BwCu1BwCl1B 120.17(5)
Cu1BwCl1BwCu1A 74.32(5)
Each copper(I) atom lies in the center of a severely distorted
950
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Fig. 5 Molecular structure of 16. Selected bond lengths and angles
are given in Table 5
Fig. 6 Molecular structure of 17. Selected bond lengths and angles
be taken as a useful indicator to estimate the strength of the
metalÈoleÐn interaction (for a non-distorted tetrahedron the
sum of these three bond angles amounts to 322.5¡). The crystal
used for the X-ray analysis contained a dinuclear copper
complex in which both phosphorus centers are located on the
same side of the mean Cu(l -Cl) Cu plane. The possible exis-
are given in Table 6
Ðned and the obtained data have limited value. Nevertheless,
some trends can be discussed. The triÑate units each use two
oxygen centers to bridge two silver centers such that an eight-
membered ring is formed, which adopts a semi anti-crown
2
2
tence of additional isomeric structures in the bulk material
was investigated by means of 31P CP-MAS NMR (vide infra).
conformation as found, for instance, in S2`. The AgwP bonds
8
[2.364(3) A; 2.358(3) A] are longer by about 0.15 A compared
to the CuwP distances in 13 but are shorter than other
reported AgwP distances (2.42 A).14a The AgwC bonds
(2.711È2.858 A) in 13 are very long when compared to the
averaged distances of many silver oleÐn complexes (2.4È2.5
A).14a,15 The very weak silverÈoleÐn interaction is well-
expressed by the sum of the two OwAgwP and OwAgwO
bond angles [Ag1: 355.5¡; Ag2: 352.3¡], which indicate only
very little displacement of the silver(I) centers from the tri-
gonal planar coordination caused by a silverÈoleÐn inter-
action. The slightly larger sums of CwPwC bond angles in 16
[&(P) \ 315.7¡] are in accord with the larger complex forma-
tion constants of silver-phosphane complexes when compared
to copper complexes.12
[Ag (l -O SOCF ) (TROPPPh) ], 16. Crystals of the
2
2
2
3 2
2
monophosphane silver compound 16 were obtained from
toluene solutions and contain one molecule of clathrated
toluene, which is shown by thin lines in Fig. 5. In the solid
state, 16 crystallizes as a neutral dinuclear complex. A
SCHAKAL view of 16 is given in Fig. 5, while relevant bond
lengths and angles are compiled in Table 5.
Owing to severe disordering of the CF groups of the
3
CF SO moieties, the structure could not be satisfactorily re-
3
3
Table 5 Selected bond lengths (A) and angles (¡) of 16
Ag1wO4
Ag1wO1
Ag1wP1
P1wC22
P1wC16
P1wC1
C1wC7
C1wC2
C7wC6
C6wC5
C2wC3
C3wC4
2.264(11)
2.358(8)
2.364(3)
1.795(13)
1.813(12)
1.880(10)
1.496(15)
1.51(2)
1.41(2)
1.45(2)
1.38(2)
1.47(2)
C5wC4
S1wO1
S1wO1
S1wO3
O2wAg2
Ag2wO5
Ag2wP2
P2wC28
C32wC31
S2wO4
S2wO5
S2wO6
1.34(2)
[Ag(TROPPPh) ]O SCF , 17. Crystals of the TROPPPh
2
3
3
1.405(10)
1.412(9)
1.417(10)
2.333(10)
2.327(11)
2.358(3)
1.860(11)
1.32(2)
silver complex 17 were obtained after recrystallization from
toluene. A SCHAKAL view of the cation of the complex is
shown in Fig. 6, selected bond lengths and angles are listed in
Table 6.
In this complex two ligand molecules are coordinated to the
silver ion and there is no contact with the triÑate counter
anion. The anion and a co-crystallized toluene molecule are
strongly disordered, which again diminishes the quality of the
data. Linearly coordinated silver-bisphosphane complexes
have been observed very often in the solid state.16 In 17, the
particular steric requirements of the TROPPPh ligand, 11a,
enforce a considerable deviation from linear coordination by
about 26¡ [PwAgwP 154.2(1)¡]. In comparsion to the mono-
phosphane complex 16, the AgwP bond distances (average:
1.361(11)
1.418(10)
1.568(11)
O4wAg1wO1
O4wAg1wP1
O1wAg1wP1
C22wP1wC16
C22wP1wC1
C16wP1wC1
C22wP1wAg1
C16wP1wAg1
C1wP1wAg1
C7wC1wC2
C7wC1wP1
C2wC1wP1
C6wC7wC1
C7wC6wC5
C3wC2wC1
C2wC3wC4
100.8(4)
127.8(3)
126.9(3)
106.0(6)
103.9(5)
105.8(5)
116.0(4)
114.5(4)
109.6(4)
115.1(9)
112.5(7)
110.7(7)
121.5(12)
125.0(12)
123.1(11)
124.7(12)
C4wC5wC6
C5wC4wC3
O2wS1wO1
O2wS1wO3
O1wS1wO3
S1wO1wAg1
S1wO2wAg2
O5wAg2wO2
O5wAg2wP2
O2wAg2wP2
C28wP2wAg2
O4wS2wO5
O4wS2wO6
O5wS2wO6
S2wO4wAg1
S2wO5wAg2
128.0(12)
128.6(13)
113.7(6)
116.5(7)
114.0(7)
119.5(5)
129.5(6)
89.6(4)
133.2(3)
129.5(3)
109.4(4)
115.9(8)
114.8(8)
113.7(7)
160.1(9)
125.4(6)
Table 6 Selected bond lengths (A) and angles (¡) of 17
AgwP2
AgwP1
P1wC1
C1wC2
2.392(2)
2.402(3)
1.868(9)
1.533(13)
C4wC5
1.333(14)
1.89
1.31
P2wC28
C31wC32
P2wAgwP1
C1wP1wAg
154.2(1)
112.3(3)
C28wP2wAg
112.0(1)
New J. Chem., 1998, Pages 947È958
951

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α
β
Scheme 4
lished and referred to as “aurophilicityÏ in many gold phos-
phane complexes and clusters.17
A further structural criterion to study the metalÈoleÐn
interaction in complexes 13, 16, 17 and 19 is change of the
boat conformation of the seven-membered ring system of the
TROPP ligand, which may be circumscribed by the angles a
and b (Scheme 4). These parameters for the uncomplexed
ligands 4 and 11a and the coinage metal complexes 13, 16, 17
and 19 are listed for comparison in Table 8.
It is clearly seen that the complexation of the metal centers
Cu`, Ag` and Au` has very little inÑuence on the boat form
when compared to that of the free ligand 11a. In the copper
complex 13, the shape of the ligand is slightly more com-
pressed and in the gold complex it is slightly widened com-
pared to free 11a. This observation corresponds with the
expectation that the copper center will bind weakly to the ole-
Ðnic moiety while the gold center shows no measurable
binding interaction. Interestingly, the sterically more encum-
bered phosphane TROPPBut, 4, has a considerably more
folded structure than 11a. This may be explained by repulsive
interactions of the spatially more extended tert-butyl groups
with the annulated benzo rings, which are thereby bent away
from the phosphorus substituents. The form of ring C in
(C H ) P, 1 (Scheme 1), in which the P center occupies the
Fig. 7 Molecular structure of 19. Selected bond lengths and angles
are given in Table 7
2.397 A) are, as expected, slightly longer. Again, the AgwC
bonds are very long [2.77(1)È2.88(1) A] and no signiÐcant
changes of the CxC distances [1.31(1) A and 1.33(1) A] com-
pared to the free ligand 11a are observed within the experi-
mental errors.
[AuCl(TROPPPh)], 19. In Fig. 7 the result of an X-ray
analysis of the gold TROPPPh complex 19 is shown; selected
bond lengths and angles are compiled in Table 7.
7
7 3
axial position as in 4 and 11a has comparable angles a and b.
NMR spectroscopy
There are no reports on authentic goldÈoleÐn complexes
and as can be seen from the almost linear PwAuwCl coordi-
nation [177.59(4)¡] in 19, any signiÐcant goldÈoleÐn inter-
action is not reÑected by an expected deviation from linear
coordination. The AuwC distances in 19 [3.095(3) and
3.286(3) A] are only slightly shorter than the sum of the van
der Waals radii (3.35 A). It might be possible that a goldÈ
oleÐn interaction can be enforced by abstracting chloride from
19 with a Lewis acid or by replacing chloride with a weakly
coordinating anion; however, attempts to isolate such a
species have failed so far. The AuwP distance [2.234(2) A] is
expectedly shorter than the AgwP distances in 16 and 17.14a
There are no further special structural features that dis-
tinguish complex 19 from other phosphane gold(I) chloride
complexes.16 No goldÈgold separations below 3.5 A are
observed in crystals of 19, which is a phenomenon often estab-
Solid
state
NMR
spectroscopy
of
[Cu (l -
2 2
Cl) (TROPPPh) ], 13. The experimental 31P solid state NMR
2
2
spectrum, recorded under the conditions of cross-polarization
and rapid rotation about the “magic angleÏ, is depicted in Fig.
8(a).
Two well-resolved “quartetÏ patterns at d [ 22 and [25 in
a ratio of ca. 8 : 3 are observed in the isotropic region of the
iso
spectrum. Based on the crystal structure analysis of 13,
showing the presence of two crystallographically inequivalent
phosphorus sites, one would also expect to Ðnd two di†erent
isotropic chemical shifts in the 31P NMR spectrum. However,
the intensity distribution actually observed makes such an
interpretation unlikely. Indeed, reconsidering the molecular
structure of 13 one Ðnds that the two sites are almost, but not
quite, related by a C symmetry. Therefore, we have to inter-
pret the spectrum as originating from either two di†erent
2
stereoisomers, for example, as E and Z forms of [Cu (l-
2
Table 7 Selected bond lengths (A) and angles (¡) of 19
Cl) (TROPPPh) ] or, alternatively, a single isomeric form
2
2
occurring in two di†erent crystallographic modiÐcations. One
of these could be as for 13, that is, containing clathrated ace-
tonitrile molecules, while the other is solvent-free. Measuring
a 31P solid state NMR spectrum immediately after re-
crystallization results in a spectrum di†erent from the one
above, showing a single, but somewhat broadened, “quartetÏ
Au1wP1
Au1wCl1
P1wC16
P1wC22
P1wC1
2.234(2)
2.300(2)
1.811(4)
1.816(5)
1.873(5)
1.512(6)
C1wC7
C2wC3
C3wC4
C4wC5
C5wC6
C6wC7
1.517(6)
1.419(6)
1.450(7)
1.329(7)
1.460(7)
1.412(7)
C1wC2
pattern at d [ 20. Subjecting this material to ageing under
P1wAu1wCl1
C16wP1wC22
C16wP1wC1
C22wP1wC1
C16wP1wAu1
C22wP1wAu1
C1wP1wAu1
C2wC1wC7
C2wC1wP1
C7wC1wP1
C2wC1wH1
C7wC1wH1
177.59(4)
108.4(2)
102.1(2)
105.0(2)
112.6(2)
113.1(2)
114.7(2)
116.3(4)
114.1(3)
109.8(3)
106(3)
P1wC1wH1
C3wC2wC1
C2wC3wC4
C5wC4wC3
C5wC4wH4
C3wC4wH4
C4wC5wC6
C4wC5wH5
C6wC5wH5
C7wC6wC5
C6wC7wC1
105(3)
iso
123.6(4)
123.6(4)
129.4(5)
114(3)
117(3)
129.9(5)
121(3)
109(3)
123.8(4)
123.0(4)
vacuum reproduces qualitatively the original two-component
Table 8 Comparison of folding angles a and b (¡) in TROPP com-
plexes and ligands
13
16
17
19
11a
4
1
M
a
b
Cu
48.3
24.6
Ag
46.6
21.7
Ag
48.9
22.6
Au
44.9
22.7
È
47.8
24.4
È
53.2
26.2
È
46.2
23.5
105(3)
952
New J. Chem., 1998, Pages 947È958

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Solid state NMR spectroscopy of [Ag (l -O SOCF )
3 2
2
2
2
(TROPPPh) ], 16. The isotropic region of the solid state
2
NMR spectrum recorded for 16 shows four discernible doub-
lets at d \ 0, [5, [8 and [13 with relative intensities of
12 :5 : 9 : 3 [see Fig. 8(b)]. Each of the doublets arises from
overlapping unresolved doublets due to the coupling to the
109Ag and 107Ag spins with a magnitude of ca. 750 Hz, which
is close to the average of 770 Hz of 1J
and 1J
31P,109Ag
31P,107Ag
observed at low temperature in CDCl solution. As a sample
3
of 16, freshly crystallized from toluene and immediately mea-
sured, showed only one doublet at d \ [9 with an averaged
Ag,P coupling constant of 778 Hz, one should assign the
former spectrum to one isomeric form of the complex conÐned
to a crystallographically variable environment.
Solid state NMR spectroscopy of [Ag(TROPPPh) ]
2
O SCF , 17. The isotropic region of the solid state NMR
3
3
spectrum of 17 consists of two sets of signals at d \ 5 and [2
[see Fig. 8(c)]. The former, being broad and of a not well-
deÐned shape, originates possibly from the overlap of two
ABM, M \ 109Ag and 107Ag, spin systems and is also present
in a freshly crystallized sample. The latter consists of a doublet
with a spacing of 503 Hz, which is in close agreement with the
average phosphorus silver couplings, that is, 522 Hz, observed
for 17 in CDCl solution and possibly represents again a dif-
3
ferent crystallographic modiÐcation of the same complex 17.
Solution NMR spectroscopy of TROPP complexes. Selected
1H, 13C and 31P NMR data of 11a, 13, 16, 17 and 19 are
listed in Table 9 for comparison.
Some signiÐcant changes are observed in the NMR data
when the free TROPPPh ligand, 11a, is complexed by a
coinage metal. As frequently observed, the 31P NMR reso-
nance is shifted towards higher frequencies with increasing
main quantum number of the metal in the order Cu \ Ag
Fig. 8 CP-MAS-31P NMR spectra of (a) copper complex 13, (b)
silver complex 16 and (c) silver complex 17
spectrum, in agreement with an assignment to di†erent crys-
tallographic modiÐcations rather than di†erent isomers.
\ Au.22 The 2J
coupling between the phosphorus
31P,1H
Each of the above mentioned “quartetsÏ is of a typical asym-
metric form, both with respect to the separations of the multi-
plet lines as well as the individual line shapes. Such patterns,
arising from the interaction of a spin 1/2 nucleus with the
spins 3/2 of the 65Cu and 63Cu nuclei, have been analyzed
before18 and a convenient Ðrst-order analysis has been
derived.19 The latter approximation allows us to estimate the
nucleus and the benzylic proton, which is small in the free
phosphane 11a, increases by about 6È10 Hz upon complex-
ation. This is an expected trend when the coordination
number at phosphorus is augmented. However, the strong
decrease of the 1J
coupling constant from 20.9 Hz in 11a
31P,13C
to 12.7 Hz in the copper complex 13 to less than 0.5 Hz in the
silver and gold complexes 16, 17 and 19 where no coupling
could be resolved, is an unexpected phenomenon and has not
been observed in transition metal complexes of (C H ) P,
scalar coupling constants 1J
and 1J
, which are
65Cu,31P
63Cu,31P
evaluated to be 1865 and 1740 Hz for the major component
and 1990 and 1860 Hz for the minor component. The magni-
tude of these coupling constants are within the range pre-
viously observed20,21 for “cubaneÏ-type tetramers of
7
7 3
1.2,10 The presence of a copper, silver or gold center in close
proximity (\2.5 A) to the CxC double bond of the hep-
tatrienyl moiety has merely an inÑuence on the chemical shift
of the 1H or 13C NMR resonances of this unit, especially
when solvent e†ects are taken into account.23 At best, a minor
low frequency shift by about 2È3 ppm can be observed in the
13C NMR spectra of the complexes. However, the rigid con-
formation of the TROPP ligand allowed, for the Ðrst time, the
estimation of a 109Ag, 1H coupling constant within an oleÐn-
silver(I) complex. In a 109Ag, 1H heteronuclear multiple
quantum coherence spectrum of complex 17 (Fig. 9) a cross-
composition CuCl(PR ), showing severely distorted tetra-
3
hedral coordination sites with a CuCl P environment. SigniÐ-
3
cantly smaller values for the parameter 1J
1270 and 940 Hz, have been found for tetrahedral CuCl P
, that is, ca.
63Cu,31P
2 2
and CuClP environments.20 This indicates that the loosely
3
coordinated double bond in 13 exerts an electronic inÑuence
on 1J
63Cu,31P
rather than that of a phosphorus ligand.
, which is similar to that of a bridging chloride
Table 9 Selected 1H, 13C and 31P NMR data of 11a, 13, 16, 17 and 19. d is vs. TMS (1H, 13C) or 85% H PO (31P). J(31P, 1H) and J(31P, 13C)
3
4
coupling constants in Hz are given in parentheses
Solvent
1H NMR
d CH(2J)
1H NMR
13C NMR
d CH(1J)
13C NMR
31P NMR
d HCxCH
d HCxCH(4J)
11a
13
16
17
19
C D
4.78 (6.1)
6.76
[7.10
6.53
6.77
[7.00
57.4 (20.9)
55.4 (12.7)
56.8 (\0.5)
55.8 (\0.5)
56.0 (\0.5)
132.7 (5.1)
128.9 (2.2)
127.8 (\0.5)
129.6 (\0.5)
129.2 (\0.5)
[14.9
[14.6
[3.0
1.5
6
6
CD CN
3
5.40 (12.6)
4.75 (15.6)
5.39 (12.3)
5.92 (16.8)
C D
6
C D
6
6
6
NC D
31.2
5
5
New J. Chem., 1998, Pages 947È958
953

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Fig. 9 109Ag,1H heteronuclear multiple quantum coherence spec-
trum of complex 17
peak due to an unresolved geminal coupling between the
109Ag spin with the 1H oleÐnic spins could be observed.
As there is an additional vicinal coupling to the phosphorus
spins, the magnitude of the parameter 2J
could be
109Ag,1H
evaluated from data obtained in a 31P,1H heteronuclear
correlation experiment and 2J amounts to ca. 0.4 Hz.
109Ag,1H
The vicinal, 3J
, coupling between the 109Ag nucleus
109Ag,1H
and the benzylic proton adjacent to the phosphorus center in
the same compound is larger, and of opposite sign, and
amounts to 7.3 Hz.
We have furthermore investigated the stability of the
silver(I) TROPPPh complexes 16 and 17 in solution by 31P
NMR spectroscopy. The spectrum of a CDCl solution of
3
complex 16 at 298 K shows one broad doublet centered at
[3.0 ppm, which is resolved into two doublets at a tem-
perature of 243 K [Fig. 10(a)]. The doublets are caused by
coupling of the 31P spin with the 107Ag (spin 1/2, 51.8%
abundance) and 109Ag (spin 1/2, 48.2% abundance) spins.
Large coupling constants of 721 Hz (1J
107Ag31P
) in 16 have been observed before for complexes in
) and 830 Hz
(1J
109Ag31P
which silver(I) binds to one tertiary phosphane ligand.24 At
the higher temperature of 323 K, only one broad resonance
signal is observed, indicating non-rigid behavior. Cross-peaks
observed between all 31P resonances in a 31P exchange spec-
trum clearly demonstrate that the exchange process is inter-
molecular in that one 31P spin is associated with both the
107Ag and the 109Ag spins. This can be explained by a
dissociation-complexation equilibrium in which the ligand
with its 31P spin is statistically distributed over both silver
spins. The displacement of the average chemical shift towards
higher frequency indicates an equilibium of the following form
involving the species 17º rather than free phosphane:
Fig. 10 (a) 31P NMR spectrum of a CDCl solution of complex 16
3
at di†erent temperatures; (b) 31P exchange spectrum of a CDCl solu-
3
tion of a mixture of complexes 16 and 17 at 298 K
[(TROPPPh)Ag(l-O SCF ) Ag(TROPPPh)]
3
3 2
16
the same cation as 17º) shows two doublets centered at 1.5
ppm in solution. The 109Ag,31P and 107Ag,31P coupling con-
stants amount to 491 Hz and 567 Hz, respectively, and lie in
the typical range observed for bisphosphane complexes of
silver.25 In solutions of pure 17, ligand-exchange processes
were not observed by NMR experiments. Adding silver tri-
H [(TROPPPh) Ag]`[Ag(O SCF ) ]~
2
3
3 2
17º
This explanation is also in agreement with the following
experiments. The bis(TROPPPh) silver complex 17 (containing
954
New J. Chem., 1998, Pages 947È958

View Article Online
Ñate, 15, to a solution of 17 leads, within the timescale of the
experiment, to rapid formation of the monophosphane
complex 16 by ligand exchange. In mixtures, both complexes
16 and 17 can be observed separately by 31P NMR spectros-
copy, indicating slow ligand exchange on the NMR timescale.
That exchange indeed takes place, could be again demon-
complexes [Cu(H CxCH )]`, [Ag(H CxCH )]` and
2
2
2
2
[Au(H CxCH )]` for which recent gas phase experiments
2
2
and theoretical investigations established a stability ordering
of Au [ Cu [ Ag.30 In TROPP-type ligands the phosphane
donor function is arranged almost orthogonally to the oleÐn
moiety of the tropylidene ring. Using the R P group as an
2
strated in
a
31P exchange spectrum where cross-peaks
anchor point, it might be possible to prepare and isolate
between all resonances were observed [Fig. 10(b)]. The slow
ligand exchange between TROPPPh silver complexes is all the
more remarkable as other silver tertiary phosphane complexes
show rapid equilibria of the form:25
models of cationic [M(R CxCR )]` complexes in the con-
2
2
densed phase, in which the oleÐnÈmetal interaction is elec-
tronically relatively unperturbed. These, as well as studies of
the oleÐn interaction with metals of the Ðrst transition metal
series (which are relatively rare), are under way. Owing to the
well-developed organic chemistry of dibenzotropylidenes,
TROPP ligands o†er the possibility to study the properties of
metal centers in electronically widely tunable but stereochemi-
cally well-deÐned environments.
(R P) Ag` H (R P) Ag` ] R P H (R P) Ag` ] 2R P
3
4
3
3
3
3
2
3
Monophosphane silver complexes of the type R PAg` were
3
not detected in these latter studies. Only for silver bisphos-
phane complexes containing a chelating ligand like cis-
Ph PCHxCHPPh could well-resolved 31P NMR spectra
2
2
showing all couplings be recorded at room temperature.26
Experimental
If an excess of triphenylphosphane Ph P is added to a
3
CDCl solution of 16, a broadened resonance signal at ]8.6
3
ppm and a broadened doublet at [1.1 ppm with a 107@109Ag
General methods
coupling of ca. 330 Hz is observed. This experiment indicates
All operations were carried out under an atmosphere of dry
and oxygen-free nitrogen by modiÐed Schlenk techniques. Sol-
vents were dried by standard methods,31 distilled and stored
under nitrogen. 1H, 13CM1HN, 19F, 31PM1HN NMR spectra
were recorded at room temperature in C D , CDCl ,
that, although exchange does occur, even a large excess of
Ph P does not liberate the TROPPPh ligand 11a from the
3
silver center to a signiÐcant extent and the most prominent
species is likely to be a [(TROPPPh)Ag(PPh )]`[O SCF ]~
3
3
3
complex. Usually, the phosphane with the smaller cone angle
6
6
3
CD CN, C D N or C D O on Bruker AC200, DPX250,
# [#(PPh ) \ 145¡] replaces the phosphane with the larger
3
5
5
4 8
3
DPX300, DRX400, AMX500 and Varian Unity-300 instru-
ments. 109Ag data were obtained in an indirect way by two-
dimensional 109Ag,1H HMQC (heteronuclear multiple
quantum coherence) spectroscopy. Chemical shifts, in ppm are
one. We have estimated27 the cone angles # of 4 and 11aÈc by
applying the trigonometric procedure developed by
Imyanitov28 using parameters from X-ray data obtained for 4
and 11a and the reported increments for phenyl (Ph), tert-
butyl (But), cyclohexyl (Cyc) and p-tolyl (pTol) substituents.
Assuming, that TROPPR, 4, and 11aÈc act as monodentate
ligands, cone angles of 210¡ (4), 185¡ (11a, b) and 201¡ (11c) are
estimated. However, regarding TROPP ligands as chelates
leads to estimations28 of much smaller cone angles of 151¡ (4),
127 (11a, b) and 143¡ (11c). These values may be com-
pared to those of bulky monodentate phosphanes like
But P (# \ 182¡) and Cy P (# \ 170¡) or of bidentate
given relative to TMS for 1H and 13C, CFCl for 19F, 85%
3
aqueous H PO for 31P and aqueous Ag` for 109Ag, extrapo-
3
4
lated to inÐnite dilution. Solid state 31P NMR spectra were
recorded by employing spinning at the “magicÏ angle, with
spinning frequencies between 2 and 14 kHz, and cross-
polarization using contact times between 0.5 and 4 ms on a
Bruker AMX400 equipped with a solid state accessory.
Chemical shifts are given relative to (NH )H PO . Melting
4
2
4
3
3
points are uncorrected, determined by sealing single crystals of
the compounds, under inert atmosphere, inside melting point
capillaries and by measuring in a melting point apparatus
According to Mr. Tottoli. Mass spectra were recorded on a
Finnigan MAT 8200 operating in either the EI (70 eV) or CI
mode. Raman spectra were recorded on a Bruker FT-IR IFS
66V equipped with a Raman accessory R106 (Neodym-YAG
Lasers, 1064 nm). IR spectra were recorded as thin Ðlms (for
liquids) between carefully dried NaCl plates, or as pellets
(powder ] KBr) on a Perkin-Elmer 783 spectrometer.
ligands like Ph PwCH wCH wPPh
(# \ 125¡) and
2
2
2
2
Cy PwCH wCH wPCy (# \ 142¡).29 One may therefore
2
2
2
2
conclude that TROPP ligands act as chelate ligands (smaller
#) and hence are not replaced by bulkier monodentate phos-
phanes.
In summary, the NMR spectroscopic results obtained for
the silver complexes 16 and 17, together with the observation
that the gold complex 19 is quantitatively formed by a ligand-
displacement reaction from Ph PAuCl, may be taken as an
3
indication of at least an increased kinetic stability of TROPPR
Precursor compounds like the dibenzo[a,d]cyclohepten-5-yl
metal complexes.
derivatives
7 and 8,32 diphenylphosphane 9a,33 ditolyl-
phosphane 9b,34,35 and dicyclohexylphosphane 9c36 (the
alcohol and the chloride) were synthesized according to the
literature. Dibenzosuberenone 6 was purchased in reagent
grade from Aldrich.
Conclusion
Dibenzo(tropylidenyl)phosphanes (TROPPR) are a new class
of phosphanes that may serve as ligands for the preparation of
cis-phosphane oleÐn metal complexes. They can be easily pre-
pared in good yields from dibenzotropylidenylchloride, 8, and
Crystallographic analysis of 4, 5, 11a, 13, 16, 17 and 19
a secondary phosphane HPR . NMR spectra of all TROPP-
2
type ligands prepared so far reveal that only one stereoisomer
The data sets for the single-crystal X-ray studies were col-
lected on Nonius CAD4 and fully automated Siemens-Stoe
AED2 four-circle di†ractometers. All calculations were per-
formed on a Digital Corporation VAX system, using the
SHELXS 86 and SHELXL 93 programs.37,38 The speciÐc
data for the crystals and the reÐnements are collected in
Tables 10 and 11. The structures were solved by direct
is formed, which is the endo isomer with the R P group axially
2
bonded to the cycloheptatrienyl moiety. The new phosphanes
are rigid and show no interconversion on the NMR timescale.
From studies of the properties of TROPPR coinage metal
complexes, it may be concluded that the complexes possess at
least an enhanced kinetic stability when compared to other
phosphane complexes. The interaction of the metal centers
Cu, Ag and Au is rather weak, as is indicated by the NMR
and structural data, and follows the order Cu [ Ag [ Au.
This is di†erent from the stability order of cationic ethylene
methods and reÐned by full-matrix least-squares on F .
2
The graphical representations of the molecular structures
were drawn using the SCHAKAL program.39 Further crystal-
lographic data (excluding structure factors) for the structures
New J. Chem., 1998, Pages 947È958
955

View Article Online
Table 10 Crystal data and structure reÐnement for 4, 5 and 11a
4
5
11a
Empirical formula
Formula weight
Temperature/K
Wavelength/A
Space group
Crystal system
Unit cell dim./A, ¡
C
H
P
C
336.43
203(2)
0.71070
P2(1)/c
Monoclinic
a \ 8.788(4), a \ 90
b \ 14.205(7), b \ 92.70(3)
c \ 16.021(8), c \ 90
1998(2)
H
P
C
376.44
H P
23 29
23 29
27 21
336.43
293(2)
0.71069
Fdd2
Orthorhombic, face-centered
a \ 23.072(5), a \ 90
b \ 37.029(7), b \ 90
c \ 9.179(2), c \ 90
7842(3)
293(2)
0.71069
P1
Triclinic
a \ 10.4162(12), a \ 93.617(8)
b \ 10.7631(11), b \ 90.830(8)
c \ 18.841(2), c \ 101.975(8)
2061.4(4)
Volume/AŽ 3
Z
16
0.141
2126
4
4
Absorption coe†./mm~1
0.139
5829
0.141
7682
ReÑections collected
Independent reÑections
Final R indices [I [ 2p(I)]
R indices (all data)
2126 [R(int) \ 0.0000]
R1 \ 0.0394, wR2 \ 0.0888
R1 \ 0.0726, wR2 \ 0.1044
5829 [R(int) \ 0.0000]
R1 \ 0.0490, wR2 \ 0.0975
R1 \ 0.0974, wR2 \ 0.1146
7246 [R(int) \ 0.0263]
R1 \ 0.0482, wR2 \ 0.1084
R1 \ 0.1246, wR2 \ 0.1446
reported in this paper have been deposited with the Fachin-
formationszentrum Karlsruhe as supplementary publication
No. CSD-406944 (4), CSD-406941 (5), CSD-406945 (11a),
CSD-406946 (13), CSD-406947 (16), CSD-406943 (17) and
CSD-406942 (19).
MHz): d 31.2 (d, 2J \ 14.1 Hz, CH ), 33.3 (d, 1J \ 33.2
PC
3
PC
Hz, CMe ), 51.6 (d, 1J \ 37.8 Hz, C ), 126.2 (s, C
), 128.8
3
PC
1
9,13
(s, C
Hz, C
), 129.4 (d, 5J \ 1.7 Hz, C
), 129.5 (d, 3J \ 2.3
11,15
PC
10,14
PC
), 132.7 (d, 4J \ 6.0 Hz, C ), 136.4 (d, 3J \ 2.8
8,12
PC
4,5
PC
Hz, C ), 140.1 (d, 2J \ 7.8 Hz, C ). 31P NMR (C D ,
3,6 PC 2,7
81.01 MHz): 26.8. MS(EI): m/z 336 (4, 5%), 191
6
6
CCDC reference number 440/054.
d
(dibenzotropyliumion, 100%), 57 (tert-butyliumion, 14%),.
(Dibenzo[a,d]cyclohepten-10-yl)di(tert-butyl)phosphane,
Synthesis of the ligands
5
(Scheme 6): yield 435 mg (48%); mp 145¡C. 1H NMR (C D ,
200.13 MHz): d 1.20 (br, 9H, CH , 1.38 (br, 9H, CH ), 3.58 (s,
2H, C H), 7.00È7.15 (m, 7H, C
3J \ 3.1 Hz, 1H, C H), 8.40 (m, 1H, C H). 13C NMR
(C D , 50.32 MHz): d 29.9 (br, CH ), 31.1 (br, CH ), 33.0 (br,
Phosphanes 4 and 5 by reaction of dibenzo-7-phosphonium-
6
6
bicyclo[2.2.2]octadiene chloride 3 with NaN(SiMe ) . One
3)
8v10
3
3 2
H and C
H), 7.61 (d,
gram (2.7 mmol) of dibenzo-7-phosphonium-bicyclo[2.2.2]
1
12v15
11
octadiene chloride4 3 was dried overnight in vacuo at 60 ¡C.
The powdered substance was then suspended in 20 ml of
toluene at [78 ¡C and 0.5 g (2.7 mmol) of sodium bistri-
methylsilylamide, dissolved in 20 ml of toluene, was added
dropwise. While warming up to ambient temperature a dark
brown solid and a bright yellow solution were formed. After 1
h stirring at ambient temperature the brown solid residue was
Ðltered o† and the yellow solution (containing only two pro-
ducts according to a 31P NMR spectrum) was reduced under
vacuum to dryness. The residue was fractionally recrystallized
from acetonitrile to yield 4 and 5. Hereby single crystals suit-
able for X-ray di†raction of both compounds could be
obtained. Performing the reaction under di†erent conditions
(other temperatures or in THF as solvent) did not alter the
results.
PH
6
5
6
3
3
3
CMe ), 41.4 (s, C ), 125.6 (d, 4J \ 1.4 Hz, C ), 125.8 (s, C ),
PC 10
126.9 (d, 4J \ 1.4 Hz, C ), 126.9 (d, 3J \ 1.7 Hz, C ),
PC PC 11
127.8 (d, 2J \ 2.0 Hz, C ), 128.0 (s, C ), 128.6 (s, C ), 129.8
1
9
8
PC
5
14
15
(s, C ), 130.4 (s, C ), 134.9 (s, C ), 139.1 (d, 3J \ 5.3 Hz,
13
12
7
PC
PR2
H
8
12
9
13
14
1
7
6
2
3
10
4
5
15
11
Scheme 5 Numbering scheme for NMR spectra of 4, 11aÈc, 13, 16,
17, 19
8
12
9
13
14
1
(Dibenzo[a,d]cyclohepten-5-yl)di(tert-butyl)phosphane
(TROPPBut), 4 (Scheme 5): yield 290 mg (32%); mp 188È
190 ¡C. 1H NMR (C D , 200.13 MHz): d 0.86 (d, 3J \ 9.7
7
2
10
6
3
4
5
15
11
6
6
PH
Hz, 18H, CH ), 4.67 (d, 2J \ 3.4 Hz, 1H, C H), 6.94 (m, 2H,
R2P
Scheme 6 Numbering scheme for NMR spectra of 5
3
PH
1
C
C
H), 6.99 (s, 2H, C H), 7.03È7.10 (m, 4H, C
H), 7.16 (m, 2H, C
H and
9,13
4,5
10,14
H). 13C NMR (C D , 75.43
11,15
8,12
6 6
Table 11 Crystal data and structure reÐnement for 13, 16, 17 and 19
13
16
17
19
Empirical formula
Formula weight
Temperature/K
Wavelength/A
Space group
Crystal system
Unit cell dim./A,¡
C
H
Cl Cu N P
C
H
Ag F O P S
2 2
C
H
AgF O P S
C
608.82
203(2)
0.71070
P2(1)/n
H AuClP
62 54
2
2
4
2
66.50 54
2
6
6
55 42
3
3
2
27 21
1115.01
1404.90
293(2)
0.71069
P2(1)/c
Monoclinic
1009.81
293(2)
0.71069
P2(1)/c
Monoclinic
a \ 20.455(4), a \ 90
b \ 17.143(3), b \ 108.00(3)
c \ 16.653(3), d \ 90
5554(2)
200(2)
0.71073
P1
Triclinic
Monoclinic
a \ 12.848(5), a \ 110.92(4)
b \ 13.826(7), b \ 96.00(4)
c \ 17.827(9), d \ 106.34(3)
2763(2)
a \ 20.708(4), a \ 90
a \ 10.378(7), a \ 90
b \ 18.350(12), b \ 92.36(5)
c \ 11.603(8), d \ 90
2208(3)
b \ 19.978(4), b \ 105.79(3)
c \ 15.561(3), d \ 90
Volume/A
Z
Ž
3
6195(2)
2
4
8
4
Absorption coe†./mm~1
0.967
15703
0.820
5939
0.502
5338
6.869
3883
ReÑections collected
Independent reÑections
Final R indices [I [ 2p(I)]
R indices (all data)
8086 [R(int) \ 0.0293]
R1 \ 0.0435, wR2 \ 0.1125
R1 \ 0.0531, wR2 \ 0.1247
5704 [R(int) \ 0.0264]
R1 \ 0.0499, wR2 \ 0.1263
R1 \ 0.1082, wR2 \ 0.1641
5149 [R(int) \ 0.0680]
R1 \ 0.0701, wR2 \ 0.1837
R1 \ 0.1089, wR2 \ 0.2259
3883 [R(int) \ 0.0000]
R1 \ 0.0253, wR2 \ 0.0586
R1 \ 0.0323, wR2 \ 0.0615
956
New J. Chem., 1998, Pages 947È958

View Article Online
C ), 139.5 (d, 3J \ 3.1 Hz, C ), 139.7 (d, 1J \ 12.8 Hz, C ),
PC PC
(dibenzotropyliumion, 100%), 178 (anthraceniumion, 48%).
2
6
4
140.4 (d, 2J \ 3.8 Hz, C ). 31P NMR (C D , 81.01 MHz): d
PC
3
6 6
Preparation of 11a (TROPPPh) using copper phosphide 12
37.5. MS(EI): m/z 336 (5, 60%), 280 (5 [ But ] H, 30%), 224
(5 [ 2But ] 2H, 100%), 191 (dibenzotropyliumion, 85%), 178
(anthraceniumion, 52%), 57 (tert-butyliumion, 22%), 43
(isopropyliumion, 30%).
Copper(I) diphenylphosphide 1211 (1.34 g, 5.4 mmol) was sus-
pended in 20 ml of THF and 1.24 g (5.4 mmol) of dibenzo[a,d]
cyclohepten-5-yl chloride 8, dissolved in 10 ml of THF, was
slowly added. After a few minutes of stirring the suspension
became a clear yellow solution. The solvent was removed
under vacuum and the yellow solid residue was suspended in
20 ml of CH Cl . A saturated aqueous solution of KCN was
Preparation of tropylidenephosphanes 11a–c
(TROPPPh), 11a. To a solution of 5.0 g (26.9 mmol) of
diphenylphosphane 9a in 20 ml of toluene, a solution of 6.1 g
(26.9 mmol) of dibenzo[a,d]cyclohepten-5-yl chloride 8 in 20
ml of toluene was slowly added at ambient temperature. A
white solid precipitated. After 1 h stirring at ambient tem-
perature the mixture was reÑuxed for 15 h under evolution of
gaseous HCl. The obtained reaction mixture was hot-Ðltered
and the solvent was removed in vacuo. The white solid residue
was then recrystallized from acetonitrile whereby colorless
crystals suitable for X-ray di†raction could be obtained. Yield
7.1 g (70%); mp 140È142 ¡C. 1H NMR (C D , 299.95 MHz):d
2
2
then added slowly and the mixture was stirred until two clear
colourless phases formed. The organic phase was separated,
dried with anhydrous Na SO and concentrated under
2
4
vacuum. The colorless solid residue was recrystallized from a
minimum amount of warm acetonitrile to yield 1.16 g (57%)
of 11a, which is soluble in toluene and dichloromethane.
Synthesis of TROPP metal complexes
[(TROPPPh) CuI Cl ] Æ 4CH CN, 13. 300 mg (0.79 mmol)
2
2
2
3
of TROPPPh, 11a was dissolved in 5 ml of acetonitrile and
added at ambient temperature to a suspension of 78 mg (0.79
mmol) of copper(I) chloride (CuCl) in ca. 30 ml of acetonitrile.
The mixture was warmed up to about 40È50 ¡C for a short
time, yielding a clear yellow solution. At 4 ¡C yellow crystals
suitable for an X-ray di†raction study were formed and Ðl-
tered o†. Yield 300 mg (68%); mp [ 224 ¡C decomposes. Anal.
6
6
4.78 (d, 2J \ 6.1 Hz, 1H, C H), 6.76 (m, 2H, C H), 6.82È
PH 4,5
6.88 (m, 8H, p-H , m-H and C H), 6.88È6.94 (m, 4H,
ph ph 10,14
H), 6.98È7.60 (m, 2H, C
1
C
H and C
H), 7.24È7.33 (m,
8,12
9,13
11,15
4H, o-H ). 13C NMR (C D , 75.43 MHz): d 57.4 (d, 1J
\
ph
6
6
PC
20.9 Hz, C ), 126.6 (d, 4J \ 1.1 Hz, C
), 128.1 (s, p-C ),
1
PC
9,13
ph
128.5 (s, m-C ), 128.6 (s, C
), 130.0 (d, 3J \ 2.2 Hz,
ph
10,14
PC
PC
C
C
C
C
), 130.6 (d, 4J \ 3.3 Hz, C
), 132.7 (d, 4J \ 5.1 Hz,
calcd for C
H
Cl Cu N P (1115.09): C, 66.78; H, 4.88; N,
8,12
PC
11,15
62 54
2
2 4 2
), 134.2 (d, 2J \ 20.9 Hz, o-C ), 135.9 (d, 3J \ 4.9 Hz,
5.02; P, 5.56; Cl, 6.36%. Found: C, 66,79; H, 4.68; N, 4.82; P,
4,5
3,6
2,7
PC
PC
ph
ph
PC
PC
), 138.2 (d, 1J \ 23.6 Hz, PC ), 138.5 (d, 2J \ 10.1 Hz,
5.78; Cl, 6.65%. 1H NMR (CD CN, 200.13 MHz): d 5.40 (d,
3
). 31P NMR (CDCl , 81.01 MHz): d [14.9. MS(EI): m/z
2J \ 12.6 Hz, 1H, C H), 7.10È7.35 (m, 16H, C H, m-,
3
PH
1
4,5
376 (11a, 25%), 191 (dibenzotropyliumion, 100%).
p-H and C
H), 7.58 (m, 4H, o-H ). 13C NMR (CD CN,
ph
8v15
ph
3
75.43 MHz): d 55.4 (d, 1J \ 12.7 Hz, C ), 128.9 (d, 4J
\
\
PC
1
PC
PC
2.2 Hz, C ), 129.1 (d, 4J \ 4.9 Hz, C
), 130.0 (d, 3J
(TROPPTol), 11b. In a similar manner, the reaction was
carried out with 3.7 g (17.7 mmol) of di-p-tolylphosphane 9b
and 4 g (17.7 mmol) of dibenzo[a,d]cyclohepten-5-yl chloride
8. Colorless crystalline needles were isolated after crys-
tallization from a mixture of acetonitrile and toluene. Yield 5.2
g (73%); mp 220È223 ¡C. 1H NMR (C D , 200.13 MHz: d
4,5
PC
9,13
9.4 Hz, C
), 130.8 (d, 5J \ 1.5 Hz, C
), 131.4 (d,
8,12
PC
10,14
4J \ 2.3 Hz, C
), 131.9 (d, 4J \ 1.7 Hz, p-C ), 132.4
PC
11,15
PC
ph
(d, 3J \ 4.9 Hz, m-C ), 133.2 (d, 1J \ 26.4 Hz, PC ),
PC
Ph
PC
ph
135.8 (d, 3J \ 15.4 Hz, C ), 136.3 (d, 2J \ 6.1 Hz, o-C ),
PC 3,6 PC ph
136.9 (d, 2J \ 3.9 Hz, C ). 31P NMR (CD CN, 81.01
PC 2,7
MHz): d [ 14.6.
3
6
6
2.00 (s, CH ), 4.93 (d, 2J \ 5.4 Hz, 1H, C H), 6.73È7.00 (m,
PH
H, C
tol 9,13 10,14
H), 7.35 (dd, 3J \ 6.9 Hz, 3J \ 6.9 Hz, o-
8,12 PH HH
H ). 13C NMR (C D , 50.32 MHz): d 21.1 (s, CH ), 57.5 (d,
tol
1J \ 20.9 Hz, C ), 126.5 (d, 4J \ 2.1 Hz, C
3
1
10H, C H, m-H , C
4,5
(m, 2H, C
H and C
H), 7.02È7.15
11,15
Preparation of (TROPPPh) AgI (O SCF ) , 16. To a solu-
3 2
tion of 100 mg (0.39 mmol) of silver(I) triÑate [Ag(O SCF ,)
2
2
3
3
3
6
1
6
3
15] in 10 ml of toluene a solution of 146.3 mg (0.39 mmol) of
TROPPPh, 11a, in 10 ml of toluene was added dropwise at
ambient temperature. After a few minutes of stirring, the
solvent was reduced under vacuum to one-third of its volume
and the solution was kept in the dark at room temperature.
The colorless crystals formed were Ðltered o† yielding 152.7
mg (62%) of 16, mp [ 160 ¡C decomposes. Before elemental
analysis, the crystals were powdered and dried under vacuum
), 128.3 (d,
PC
PC
9,13
3J \ 1.3 Hz, m-C ), 128.9 (s, C
), 130.0 (d, 3J \ 2.2
PC
Hz, C
8,12
tol
10,14 PC
), 130.7 (d, 4J \ 3.2 Hz, C
), 132.7 (d, 4J \ 4.8
PC
11,15
PC
Hz, C ), 134.3 (d, 2J \ 20.9 Hz, o-C ), 134.8 (d, 1J
\
4,5
PC
tol
PC
20.7 Hz, PC ), 135.9 (d, 3J \ 5.2 Hz, C ), 138.3 (s, CH -
tol PC 3,6
C ), 138.5 (d, 2J \ 9.6 Hz,
tol PC
3
).
C2,7
31P NMR (C D , 81.01 MHz): d [16.4. MS(EI): m/z 404
6
6
(11b, 30%), 191 (dibenzotropyliumion, 100%).
for 36 h. Anal. calcd for C
H Ag F O P S (1266.76): C,
56 42 2 6 6 2 2
53.10; H, 3.34%. Found: C, 52.59; H, 3.38%. 1H NMR
(TROPPCyc), 11c. In a similar manner, the reaction was
carried out with 1.5 g (7.5 mmol) dicyclohexylphosphane 9c
and 1.7 g (7.5 mmol) of dibenzo[a,d]cyclohepten-5-yl chloride
8. Colorless needles crystallized from acetonitrile. Yield 2.4 g
(82.5%); mp 184È185 ¡C. 1H NMR (C D , 200.13 MHz): d
(C D , 200.13 MHz): d 4.75 (d, 2J \ 15.6 Hz, 1H, C H),
6
6
PH
1
H), 6.80 (t,
6.53 (s, 2H, C H), 6.72 (t, 3J \ 7.3 Hz, 2H, C
4,5
3J \ 7.6 Hz, 2H, C
HH
HH
9,13
H), 6.88 (br, 4H, m-H ), 6.95È7.02
H), 7.06È7.20 (m, 6H, p-H and o-H ), 7.42 (s,
10,14
ph
(m, 2H, C
11,15
ph
ph
2H, C
127.8 (s, C ), 128.5 (s, C
130.8 (s, C
H). 13C NMR (C D , 75.43 MHz): d 56.8 (s, C ),
6
6
8,12
6
6
1
0.87È1.18 (brm, 8H, H ), 1.20È1.40 (brm, 6H, H ), 1.53È1.60
cyc cyc
(brm, 6 H, H ), 1.78È1.84 (brm, 2H, CP-H ), 4.50 (d, 2J
cyc cyc
4.9 Hz, 1H, C H), 6.95 (s, 2H, C H:), 7.00È7.20 (m, 8H,
4,5
H). 13C NMR (C D , 75.43 MHz): d 26.9 (s, p-C ), 27.9
8v15 cyc
(d, 3J \ 10.4 Hz, m-C ), 28.1 (d, 3J \ 7.7 Hz, m-C ),
PC cyc PC cyc
30.0 (d, 2J \ 8.8 Hz, o-C ), 31.2 (d, 2J \ 17.5 Hz, o-C ),
), 128.7 (s, C
9,13
), 129.3 (s, C
),
4,5
11,13
10,14
8,12
\
), 130.9 (s, p-C ), 131.5 (s, m-C ), 131.7 (d,
PH
ph
ph
2J \ 4.0 Hz, o-C ), 134.0 (d, 2J \ 2.5 Hz, C ), 134.4 (d,
PC ph PC 3,6
1J \ 16.1 Hz, PC ), 134.8 (d, 2J \ 6.4 Hz, C ). 19F
1
C
6
6
PC
ph
PC
2,7
NMR (CDCl , 75.43 MHz): d [77.7. 31P NMR (CDCl ,
3
3
81.012 MHz): d [3.0 (dd, 1J
\ 720.7 Hz, 1J
\
PC
cyc
PC
cyc
107AgP
109AgP
35.3 (d, 1J \ 23.6 Hz, PC ), 52.2 (d, 1J \ 26.9 Hz, C H),
829.2 Hz.
PC
cyc
PC
), 128.6 (s, C
1
126.4 (d, 4J \ 0.8 Hz, C
), 129.6 (d,
), 132.6 (d,
PC
9,13
10,14
3J \ 1.8 Hz, C
), 129.9 (d, 4J \ 0.7 Hz, C
[(TROPPPh) AgI ]O SCF , 17. Complex 17 was prepared
2 3 3
PC
PC
8,12
4,5
PC
PC
11,15
4J \ 3.3 Hz, C ), 136.1 (d, 3J \ 2.6 Hz, C ), 139.8 (d,
like 16 but using 15 and 11a in a 1 : 2 stoichiometry [250 mg
(0.97 mmol) 15 and 730.5 mg (1.95 mmol) 11a; each com-
ponent dissolved in 10 ml of toluene]. Colorless single crystals
suitable for X-ray di†raction were obtained by slow di†usion
3,6
2J \ 5.5 Hz, C ). 31P NMR (C D , 81.01 MHz): d [3.2.
PC 2,7
MS(EI): m/z 388 (11c, 70%), 306 (11c [cyclohexyl ] H, 95%),
6
6
224 (11c[2 cyclohexyl ] 2 H, 20%), 191
New J. Chem., 1998, Pages 947È958
957

View Article Online
6 (a) H. Auterho†, J. Knabe and H.-D. Holtje, L ehrbuch der Phar-
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7 T. Asao and M. Oda, in Houben-W eyl Methoden der Organischen
Chemie, Thieme, New York, 1985, vol. 5/2c, pp. 739È744.
8 M. Herberhold, private communication and K. Bauer, disser-
tation, University of Bayreuth 1995.
9 J. L. Wardell, in Comprehensive Coordination Chemistry II, ed. E.
W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon, Oxford,
1995, vol. 3, pp. 1È133.
10 T. H. Lemmen, G. V. Goeden, J. C. Hu†man, R. L. Geerts and K.
G. Caulton, Inorg. Chem., 1990, 29, 3680.
of hexane into a solution of complex 17 in toluene. This com-
pound has to be stored as well in the dark. Yield of
C
H
AgF O P S (1009.81): 931 mg (95%); mp [ 150 ¡C
55 42
3 3 2
decomposes. 1H NMR (CDCl , 200.13 MHz):d 5.48 (A parts
3
of 2 AA@MM@X spin systems, 4J ] 2J \ 12 Hz, 3J
\
PH
PH
AgH
7.0 Hz, 1H, C H), 6.74 (s, 2J \ 1 Hz, 2H, C H), 7.15 (m,
1
AgH
4,5
C
H), 7.18 (m, C
H), 7.21 (m, p-C H), 7.31 (m, o-
8,12
9,13,10,14
ph
C H and m-C H), 7.42 (m, C
H). 13C NMR (CDCl ,
ph ph 11,15
3
PC
75.43 MHz): d 55.3 (A parts of 2 AMM@X systems, 1J
] 3J \ 15 Hz, J B 2 Hz, C ), 121.2 (q, 1J \ 321 Hz,
PC AgC FC
CF ), 128.0 (br s, p-C ), 128.4 (m, A parts of 2 AMM@X
ph
systems, 1J ] 3J \ 31.4 Hz, J B 5 Hz, PC ), 129.0 (A
1
3
11 C. Meyer, H. Grutzmacher and H. Pritzkow, Angew. Chem., 1997,
109, 2576; Angew. Chem., Int. Ed. Engl., 1997, 36, 2471 and refer-
ences cited therein.
PC
PC
AgC
ph
parts of 2 AMM@X systems, 3J ] 5J \ 10.1 Hz, m-C )??,
PC
PC
ph
), 131.3 (s,
9,13
129.4 (br m, C ), 130.3 (s, C
), 130.4 (s, C
4,5
10,14
12 G. L. Lewandos, D. K. Gregstone and F. R. Nelson, J. Organomet.
C
), 131.7 (br m, A parts of 2 AMM@X systems, 3J
Chem., 1976, 118, 363.
11,15
PC
] 5J \ 5 Hz, C
), 133.4 (br m, A parts of 2 AMM@X
13 J. H. van Hende and W. C. Bird, J. Am. Chem. Soc., 1963, 85, 1009.
14 (a) For a review see: A. G. Orpen, L. Brammer, F. H. Allen, O.
Kennard, D. G. Watson and R. Taylor, J. Chem. Soc., Dalton
T rans, 1989, S1; (b) M. R. Churchill and F. J. Rotella, Inorg.
Chem., 1979, 18, 167; (c) P. H. Davis, R. L. Belford and I. C. Paul,
Inorg. Chem., 1973, 12, 213.
PC
8,12
PC
systems, 3J ] 5J \ 5 Hz, C ), 133.8 (m, A parts of 2
PC
3,6
AMM@X systems, 2J ] 4J \ 16 Hz, J \ 2.2 Hz, o-
PC PC AgC
PC ), 133.9 (br m, C ). 19F NMR (CDCl , 75.429 MHz): d
ph
2,7
3
[77.7. 31P NMR (CDCl , 202.46 MHz):
d 2.6 (2 d,
3
1J
\ 491 Hz, 1J
\ 567 Hz). 109Ag NMR (CDCl ,
107AgP
109AgP
3
15 Review on silver oleÐn complexes: C. D. M. Beverwijk, G. J. M.
van den Kerk, A. J. Leusink and J. G. Noltes, Organomet. Chem.
Rev. A, 1970, 5, 215.
23.29 MHz, Ag` ): d 905.4 (t, 1J \ 567 Hz).
aq
AgP
16 N. C. Baenziger, W. E. Bennet and D. M. Soboro†, Acta Crystal-
logr., Sect. B, 1976, 32, 962; P. F. Barron, L. M. Engelhardt, P. C.
Healy, J. Oddy and A. H. White, Aust. J. Chem., 1987, 40, 1545.
17 H. Schmidbaur, Gold Bull., 1990, 23, 11.
(TROPPPh)AuICl, 19. 250 mg (0.505 mmol) of tri-
phenylphosphane gold(I) chloride 18 was suspended in 20 ml
of toluene. After addition of 190 mg (0.505 mmol) of
TROPPPh in 10 ml of toluene the solid dissolved. A few
minutes later a colorless solid precipitated. It was separated
by Ðltration and dried under vacuum. Upon adding some ace-
tonitrile and warming the suspension up to about 40 ¡C the
solid dissolved again. At 4 ¡C the product crystallized in color-
less, well-designed cubes, which could be used for single
18 E. M. Menger and W. S. Veeman, J. Magn. Reson., 1982, 46, 257.
19 A. C. Olivieri, J. Magn. Reson., 1989, 81, 201.
20 P. F. Barron, J. C. Dyason, L. M. Engelhardt and P. C. Healy,
Inorg. Chem. 1984, 23, 3766.
21 S. Attar, G. A. Bowmaker, N. W. Alcock, J. S. Frye, W. H.
Bearden and J. H. Nelson, Inorg. Chem., 1991, 30, 4743.
22 P. S. Pregosin, in Methods in Stereochemical Analysis, ed. J. G.
Verkade and L. D. Quin, VCH, New York, 1987, vol. 8, pp. 465È
530.
23 B. E. Mann and B. F. Taylor, 13C NMR Data for Organometallic
Compounds, Academic Press, London, 1981, pp. 184È199.
24 F. Lianza, A. Macchioni, P. S. Pregosin and H. Ruegger, Inorg.
Chem., 1994, 33, 4999.
25 E. L. Muetterties and C. W. Alegranti, J. Am. Chem. Soc., 1972, 94,
6386.
crystal X-ray di†raction. Yield of C
H
AuClP (608.82): 221
27 21
mg (71.8%); mp [ 280 ¡C decomposes. 1H NMR (pyridine-d ,
5
200.13 MHz): d 5.92 (d, 2J \ 16.8 Hz, 1H, C H), 7.00È7.35
PH
1
(m, 16H, m-, p-H and C
H, C H), 7.81 (ddd, 4J \ 1.7
ph
8v15
4,5
HH
Hz, 3J \ 8.2 Hz, 3J \ 12.0 Hz, 4H, o-H ). 13C NMR
HH
PH
ph
(pyridine-d , 50.32 MHz): d 56.0 (d, 1J \ 29.6 Hz, C ), 128.3
5
PC
1
4,5
(d, 3J \ 2.5 Hz, C
), 129.0 (s, C
), 129.2 (s, C ), 129.3
PC
9,13
10,14
(d, 4J \ 1.2 Hz, p-C ), 131.0 (d, 3J \ 2.6 Hz, C
),
26 S. J. Berners-Price, P. J. Sadler, C. Brevard and A. Pagelot, Inorg.
PC
ph
PC
11,15
Chem., 1985, 24, 4278.
131.8 (d, 2J \ 5.7 Hz, C
), 132.0 (d, 3J \ 3.1 Hz, m-C ),
PC
PC
8,12 PC ph
27 J. Thomaier, Dissertation, University of Freiburg, 1996.
28 (a) N. S. Imiyanitov, Sov. J. Coord. Chem., 1985, 11, 1041; Engl.
Ed., 1985, 597; (b) N. S. Imiyanitov, Sov. J. Coord. Chem., 1985, 11,
1171; Engl. Ed., 1985, 663.
133.7 (d, 2J \ 6.3 Hz, o-C ), 133.7 (d, 3J \ 1.6 Hz, C ),
ph
ph
PC
PC
3,6
2,7
135.0 (d, 1J \ 13.6 Hz, PC ), 135.9 (d, 2J \ 8.8 Hz, C ).
PC
31P NMR (pyridine-d , 81.01 MHz): d 31.2.
5
29 C. A. Tolman, Chem. Rev., 1977, 77, 315.
30 (a) E. R. Fisher and P. B. Armentrout, J. Phys. Chem., 1990, 111,
4251; (b) B. C. Guo and A. W. Castleman, Jr., Chem. Phys. L ett.,
1991, 181, 16; (c) D. Schroder, J. Hrusak, R. H. Hertwig, W. Koch,
P. Schwerdtfeger and H. Schwarz, Organometallics, 1995, 14, 312;
(d) R. H. Hertwig, W. Koch, D. Schroder, H. Schwarz, J. Hrusak
and P. Schwerdtfeger, J. Phys. Chem., 1996, 100, 12253 and refer-
ences cited therein.
Acknowledgement
This work was supported by the Swiss National Science
Foundation and the ETH Zurich. We thank Prof. Dr. P. S.
Pregosin (ETH Zurich) and Prof. Dr. L. M. Venanzi (ETH
Zurich) for many helpful comments.
31 D. D. Perrin, W. L. F. Armarego and D. R. Perrin, PuriÐcation of
L aboratory Chemicals, 2nd edn., Pergamon Press, Oxford, 1980.
32 G. Berti, J. Org. Chem., 1957, 22, 230.
33 W. Kuchen and H. Buchwald, Chem. Ber., 1958, 91, 2837.
34 P. D. Bartlett and G. Meguerian, J. Am. Chem. Soc., 1956, 78,
3710.
35 D. Wittenberg and H.Gilman, J. Org. Chem., 1958, 23, 1063.
36 H. M. Walborsky, J. Am. Chem. Soc., 1992, 114, 3455.
37 G. M. Sheldrick, SHEL XL 93, Program for Crystal Structure
Determination, University of Gottingen, 1993.
38 G. M. Sheldrick, SHEL XS 86, University of Gottingen, 1986.
39 E. Keller, SCHAKAL 88B/V 16, Kristallographisches Institut der
Universitat Freiburg, 1988.
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