Reactivity of an acetylenephosphino gold(III) precursor: Addition to the triple bond or formation of alkynyl derivatives

Article abstract of DOI:10.1021/om010385+

We have synthesized the gold(III) complex Au(C₆F₅)₃(PPh₂CCH) (1), containing an acetylene moiety. Reactions with sodium alkoxides lead chemoselectively and regioselectively to gold(III) complexes containing the new ligand (2-alkoxyethenyl)diphenylphosphine or (2,2-dialkoxyethyl)diphenylphosphine, via a single or double alcohol addition to the acetylenephosphine fragment. Reaction of complex 1 with gold(I) or silver(I) acetylacetonato derivatives affords di-, tri-, or tetranuclear alkynylphosphino complexes, namely Au^III(C₆F₅)₃ (PPh₂CC)-M^I(PPh₃) (M = Au, Ag), {Au^III(C₆F₅)₃ (PPh₂CC)}₂Au^I and {Au^III(C₆F₅)₃(PPh₂CC) Au^I}₂ (μ-PPh₂CH₂CH₂ PPh₂). The crystal structures of Au(C₆F₅)₃(PPh₂CH₂ CH(OMe)₂) and Au^III (C₆F₅)₃(PPh₂CC)Au^I (PPh₃) have been determined by X-ray diffraction studies. Luminescence studies in the solid state show that only the tetranuclear derivative is luminescent at room temperature.

Full text of DOI:10.1021/om010385+

3906
Organometallics 2001, 20, 3906-3912
Rea ctivity of a n Acetylen ep h osp h in o Gold (III)
P r ecu r sor : Ad d ition to th e Tr ip le Bon d or F or m a tion of
Alk yn yl Der iva tives
Manuel Bardaj´ı and Antonio Laguna*
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
Peter G. J ones
Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t,
Postfach 3329, D-38023 Braunschweig, Germany
Received May 11, 2001
We have synthesized the gold(III) complex Au(C6F5)3(PPh2CCH) (1), containing an acetylene
moiety. Reactions with sodium alkoxides lead chemoselectively and regioselectively to gold-
(III) complexes containing the new ligand (2-alkoxyethenyl)diphenylphosphine or (2,2-
dialkoxyethyl)diphenylphosphine, via a single or double alcohol addition to the acetylene-
phosphine fragment. Reaction of complex 1 with gold(I) or silver(I) acetylacetonato derivatives
affords di-, tri-, or tetranuclear alkynylphosphino complexes, namely AuIII(C6F5)3(PPh2CC)-
MI(PPh3) (M ) Au, Ag), {AuIII(C6F5)3(PPh2CC)}2AuI, and {AuIII(C6F5)3(PPh2CC)AuI}2(µ-PPh2-
CH2CH2PPh2). The crystal structures of Au(C6F5)3(PPh2CH2CH(OMe)2) and AuIII(C6F5)3(PPh2-
CC)AuI(PPh3) have been determined by X-ray diffraction studies. Luminescence studies in
the solid state show that only the tetranuclear derivative is luminescent at room temperature.
In tr od u ction
to the terminal alkyne, followed by that of a gold(I) halo
derivative. Recently some other specific reagents have
been used, such as [Au(NH3)2]+ or the more generally
applicable acetylacetonato gold(I) complexes, which
already contain the base in the gold precursor.3 Alkynyl
gold(I) complexes have shown interesting optical prop-
erties, and generally the ancillary ligands are phos-
phines.4 Thus, it would be promising to use phosphi-
noalkynyl ligands to study luminescence properties.
Accordingly, in this work we have prepared the
acetylenephosphino gold(III) complex Au(C6F5)3(PPh2-
CCH), from which we have tried to synthesize poly-
nuclear acetylide derivatives by reaction with sodium
alkoxide (methoxide, ethoxide) and chloro derivatives;
unexpectedly, we have observed single and double
alcohol addition to the triple bond, which to the best of
our knowledge had not previously been reported in
Phosphinoalkynes, PR2CCR′, are potentially bifunc-
tional ligands, able to coordinate as a phosphine, an
acetylene, or a combination of both; additionally, if R′
) H, the ligand can also act as an acetylide, by
deprotonation of the CtCH group. The coordination via
the phosphorus lone pair usually dominates, mainly in
complexes of metals in their normal oxidation states,
although derivatives have been reported where this
ligand behaves as a six- or even seven-electron (in the
case of R ) H) donor.1 In some cases the alkyne
fragment undergoes M-H or M-C insertion reactions,
oxidative alkyne coupling processes, and even cleavage
of the P-C bond to yield phosphide and alkynyl frag-
ments that can give further reactions.2
There has been considerable activity concerning the
synthesis of alkynylgold(I) derivatives. They can be
prepared in various ways, but the most typical is the
addition of a base, such as sodium alkoxide, in alcohol
(3) (a) Schmidbaur, H.; Grohmann, A.; Olmos, M. E. In Gold:
Progress in Chemistry, Biochemistry and Technology; Schmidbaur, H.,
Ed.; Wiley: New York, 1999; p 654. (b) Alejos, P.; Coco, S.; Espinet, P.
New J . Chem. 1995, 19, 799. (c) Mingos, D. M. P.; Yau, J .; Menzer, S.;
Williams, D. J . Angew. Chem., Int. Ed. Engl. 1995, 34, 1894. (d)
Vicente, J .; Chicote, M. T.; Abrisqueta, M. D. J . Chem. Soc., Dalton
Trans. 1995, 497. (e) MacDonald, M.-A.; Puddephatt, R. J .; Yap, J . P.
A. Organometallics 2000, 19, 2194.
(4) (a) Yam, V. W.-W.; Lo, K. K.-W.; Wong, K. M.-C. J . Organomet.
Chem. 1999, 578, 3 and references therein. (b) Li, D.; Hong, X.; Che,
C.-M.; Lo, W.-C.; Peng, S.-M. J . Chem. Soc., Dalton Trans. 1993, 2929.
(c) Yam, V. W.-W.; Choi, S. W.-K. J . Chem. Soc., Dalton Trans. 1996,
4227. (d) Mu¨ller, T. E.; Choi, S. W.-K.; Mingos, D. M. P.; Murphy, D.;
Williams, D. J .; Yam, V. W.-W. J . Organomet. Chem. 1994, 484, 209.
(e) Irwin, J .; Vittal, J . J .; Puddephatt, R. J . Organometallics 1997, 16,
3541. (f) Hunks, W. J .; MacDonald, M.-A.; J ennings, M. C.; Puddephatt,
R. J . Organometallics 2000, 19, 5063. (g) Yam, V. W.-W.; Cheung, K.-
L.; Yuan, L.-H.; Wong, K. M.-C.; Cheung, K.-K. Chem. Commun. 2000,
1513.
(1) (a) Went, M. J . Polyhedron 1995, 14, 465 and references therein.
(b) Dickson, R. S.; Simone, T.; Parker, R. J .; Fallon, G. D. Organo-
metallics 1997, 16, 1531. (c) Ara, I.; Falvello, L. R.; Ferna´ndez, S.;
Fornie´s, J .; Lalinde, E.; Mart´ın, A.; Moreno, M. T. Organometallics
1997, 16, 5923. (d) Bruce, M. I.; Williams, M. L.; Patrick, J . M.; White,
A. H. J . Chem. Soc., Dalton Trans. 1985, 1229.
(2) (a) Charmant, J . P. H.; Fornie´s, J .; Go´mez, J .; Lalinde, E.;
Moreno, M. T.; Orpen, A. G.; Solano, S. Angew. Chem., Int. Ed. 1999,
38, 3058. (b) Bennett, M. A.; Cobley, C. J .; Wenger, E.; Willis, A. C.
Chem. Commun. 1998, 1307. (c) Mahieu, A.; Miquel, Y.; Igau, A.;
Donnadieu, B.; Majoral, J .-P. Organometallics 1997, 16, 3086. (d)
Adams, C. J .; Bruce, M. I.; Liddell, M. J .; Skelton, B. W.; White, A. H.
Organometallics 1992, 11, 1182. (e) Miquel, Y.; Igau, A.; Donnadieu,
B.; Majoral, J .-P.; Dupuis, L.; Pirio, N.; Meunier, P. J . Am. Chem. Soc.
1998, 120, 3504.
10.1021/om010385+ CCC: $20.00 © 2001 American Chemical Society
Publication on Web 08/08/2001

An Acetylenephosphino Gold(III) Precursor
Organometallics, Vol. 20, No. 18, 2001 3907
Sch em e 1
Ta ble 1. Selected 1H a n d 31P {1H} NMR Reson a n ces
for Com p lexes 1-5a
metal complexes. We have also prepared for the first
time (2-alkoxyethenyl)diphenylphosphines, although
they are coordinated to a metal center. We have
characterized by X-ray diffraction the final product of
this reaction in the case of methoxide, namely Au-
(C6F5)3(PPh2CH2CH(OMe)2), the first complex contain-
ing this phosphine to be structurally characterized. We
have also prepared the “expected” mixed di-, tri-, and
tetranuclear derivatives containing phosphino gold(III)
and acetylide gold(I) or silver(I) fragments by using the
“acac method”,5 and we have determined the crystal
structure of AuIII(C6F5)3(PPh2CC)AuI(PPh3).
1H
complex
HR
Hâ
Rb
31P{1H}
1
3.51 d
5.20 dd 6.90 dd
5.15 “t” 7.02 dd
2.88 dd 4.28 “q” 3.11
5.25 dd 7.06 dd
5.10 dd 6.95 dd
-2.6
9.0
-1.6
10.6
8.5
2a
2b
3
4a
4b
5
3.84
4.01
1.43 t, 4.10 q
1.15 t, 3.99 q
1.1
11.4
2.89 dd 4.33 “q” 0.96 t, 3.11 m, 3.40 m
a
In CDCl3; proton assignment -Au-PPh2-CHRx-CHâ(OR)x
b
(x ) 0-2). R ) Me for complexes 2 and 3; R ) Et for complexes
4 and 5.
Resu lts a n d Discu ssion
2b and 4a /4b. Selective phosphorus decoupling, 1H{31P}
NMR, and COSY experiments have been carried out to
determine fully the relationships, the chemical shifts,
and the coupling constants. The mixtures for the
ethenyl-phosphino complexes can be assigned to the
trans/cis isomers, whereby the main product is the trans
Syn th esis a n d Ch a r a cter iza tion of Au (C6F 5)3-
(P P h 2CCH) a n d Rea ctivity tow a r d Alk oxid es. The
reaction of ethynyldiphenylphosphine with Au(C6F5)3-
(tht) (tht ) tetrahydrothiophene) led by displacement
of tht to complex 1 with the acetylenephosphine ligand
coordinated only through the phosphorus donor atom
(Scheme 1). We have carried out the reaction of complex
1 with sodium methoxide, and surprisingly, we obtained
complex 2 as a mixture of isomers (cis/trans) containing
the new phosphine (2-methoxyethenyl)diphenylphos-
phine, coming from the anti-Markovnikov addition of
methanol to the noncoordinated alkyne fragment. The
addition of an excess of NaOMe to complex 1 led after
1 week to the (2,2-dimethoxyethyl)diphenylphosphino
complex 3, through a double anti-Markovnikov metha-
nol addition. Analogous results were obtained by using
sodium ethoxide, involving single or double anti-Mark-
ovnikov addition of ethanol to give complexes 4 and 5.
Complexes 1-5 are air- and moisture-stable white
solids. The IR spectrum of 1 shows a strong absorption
at 3209 cm-1 from ν(CtCH) and a signal at 2071 cm-1
from the asymmetric CtC, which are not present for
the other derivatives; all the spectra show absorptions
corresponding to the pentafluorophenyl rings around
965 and 800 cm-1.6 Their acetone solutions are noncon-
ducting. Selected 1H and 31P{1H} NMR data are col-
lected in Table 1. The 31P{1H} NMR spectra display a
single resonance. The proton spectrum of 1 shows the
acetylenephosphine ligand with a characteristic doublet
(3J HP ) 9.3 Hz) due to PCtCH, which disappears after
reaction with alkoxide. The proton spectra of complexes
2 and 4 show two products in ratios of ca. 80:20 and
70:30, respectively, for the mixtures of derivatives 2a /
isomer, because of the greatest H-H coupling (3J HH
)
ca. 13.5 Hz) and the smallest P-H coupling (3J HP ) 10.6
1
and 12.5 Hz for derivatives 2a and 4a ). Finally, the H
NMR spectra of complexes 3 and 5 show a single
product, which must be the isomer PPh2CH2CH(OR)2,
because only one kind of alkoxide and two types of H in
the ratio 1:2 are observed (in fact, for complex 5 with R
) OCH2CH3 one observes one resonance for CH3 but
two resonances for CH2, which are attributable to
diastereotopic protons as confirmed by a COSY experi-
ment).
The 19F NMR spectra show the pattern of one Au-
(C6F5)3 unit (two types of C6F5 rings in a 1:2 ratio) for
complexes 1, 3, and 5 and of two different Au(C6F5)3
units in the case of 2 and 4 (as expected for the mixture
2a /2b and 4a /4b). The reaction was monitored by NMR
to verify that the first alcohol addition takes place very
fast and only the starting complex 1, 2a , and 2b (or 3a
and 3b) are observed, but the second one occurs very
slowly after adding an excess of alkoxide; a mixture of
complexes 2a , 2b, and 3 (or 4a , 4b, and 5) is observed,
which finally leads to the double-addition complex 3 (or
5).
The FAB- mass spectra show a peak corresponding
to [Au(C6F5)2]- as the base peak and a peak for complex
1 at m/z 907 due to [M - H]-. In the FAB+ mass spectra
the fragments [Au(PPh2R)]+ are observed, which are
useful because the different phosphines can be distin-
guished. The peaks for 1-5 are as follows: m/z (%
abundance, R) 407 (100, CtCH), 439 (100, CHd
CHOMe), 471 (48, CH2CH(OMe)2), 453 (100, CHd
CHOEt), and 499 (37, CH2CH(OEt)2).
(5) Vicente, J .; Chicote, M. T. Coord. Chem. Rev. 1999, 193-195,
1143.
(6) Uso´n, R.; Laguna, A.; Garc´ıa, J .; Laguna, M. Inorg. Chim. Acta
1979, 37, 201.

3908 Organometallics, Vol. 20, No. 18, 2001
Bardaj´ı et al.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 3
Au-C(41)
Au-C(51)
Au-C(31)
Au-P
P-C(11)
P-C(21)
2.065(3)
2.068(3)
2.067(3)
2.3692(8)
1.810(3)
1.824(3)
P-C(1)
1.835(4)
1.509(5)
1.360(5)
1.414(5)
1.414(5)
1.398(6)
C(1)-C(2)
C(2)-O(1)
C(2)-O(2)
C(3)-O(1)
C(4)-O(2)
C(41)-Au-C(51) 171.15(11) C(11)-P-Au
108.92(11)
112.12(10)
115.56(12)
114.5(3)
C(41)-Au-C(31)
C(51)-Au-C(31)
C(41)-Au-P
87.62(11) C(21)-P-Au
88.60(11) C(1)-P-Au
90.17(8)
94.24(9)
174.78(9)
C(2)-C(1)-P
O(1)-C(2)-O(2) 113.8(3)
O(1)-C(2)-C(1) 108.7(3)
C(51)-Au-P
C(31)-Au-P
C(11)-P-C(21)
C(11)-P-C(1)
C(21)-P-C(1)
104.40(14) O(2)-C(2)-C(1) 112.7(4)
110.70(16) C(2)-O(1)-C(3) 113.6(4)
104.54(16) C(4)-O(2)-C(2) 115.0(3)
CAuP angles ranging from 87.62(11) to 94.24(9)°. The
acetylenephosphine starting ligand has clearly changed
by the formal addition of two methanol molecules to the
triple bond. The C(1)-C(2) distance is 1.509(5) Å,
consistent with a single bond, and compares well to the
corresponding single carbon-carbon bond in the
isopropyl substituent in the related AuCl(iPr2PCCH)
(1.510(12)-1.526(13) Å);7 it is clearly different from the
carbon-carbon triple bond in the same derivative
(1.204(7) Å). A search of the Cambridge Crystallographic
Database for the acyclic fragment CH2CH(OC)2 yielded
25 hits with a mean C-C bond length of 1.507 Å. The
C(2)-O distances are 1.360(5) and 1.414(5) Å. All of the
bonds may be slightly vibrationally shortened, because
the U values of the dimethoxyethyl fragment are
marginally higher than in the rest of the molecule,
although none of the values are strikingly high (maxi-
mum Ueq 0.079 Å2 for C3). There are no significant
differences in the P-C distances, which lie in the range
1.810(3)-1.835(4) Å.
Au-C bond distances trans to the phosphine and
trans to pentafluorophenyl are almost equal, 2.067(3)
and 2.065(3), 2.068(3) Å, respectively. They are shorter
than those found in Au(C6F5)3{PPh(CH2PPh2)2}
(2.078(6)-2.082(7) Å)9 but similar to those found in
other tris(pentafluorophenyl)gold(III) complexes, such
as [Au(C6F5)3(S2C-PEt3)] (2.067(4) and 2.076(4) Å trans
to C),10 [(µ-S2C-PEt3){Au(C6F5)3}2] (2.062(14)-
2.090(13)Åtrans toC),10 NBu4[{Au(C6F5)3PPh2CHPPh2}2-
Au] (2.063(8) and 2.080(8) trans to P, 2.057(8)-2.069-
(9) Å trans to C),11 and [N(PPh3)2][{Au(C6F5)3(µ-PPh2)}2-
Au] (2.073(6) Å trans to P, 2.052(5) and 2.058(6) Å trans
to C).12 The AuIII-P bond distance is 2.3692(8) Å, similar
to those found in NBu4[{Au(C6F5)3PPh2CHPPh2}2Au]
(2.367(2) Å)11 and in [N(PPh3)2][{Au(C6F5)3(µ-PPh2)}2-
Au] (2.365(2) Å),12 shorter than in [Au(C6F5)3{PPh2C-
(dCH2)PPh2}Au(C6F5)] (2.382(2) Å),13 but longer than
reported in AuMe3PPh3 (2.350(6) and 2.347(6) Å)14 or
F igu r e 1. Molecular structure of complex 3, Au(C6F5)3-
(PPh2CH2CH(OMe)2).
In contrast to our findings, it has been reported that
the reaction of the gold(I) derivative AuCl(PR2CCH)
with NaOMe/MeOH leads, as expected, to the deproto-
nation of the terminal alkyne and the formation of [Au-
(PR2CC)]n as insoluble polymeric chains.7 In our case
the formation of this polymer is prevented because of
the high stability of the tris(pentafluorophenyl)gold
fragment, and the acetylenic fragment is activated for
nucleophilic attack. More closely related to our reaction
are the reported alcohol additions to alkynes catalyzed
by a gold(I) or a gold(III) derivative or to an olefinic
double bond activated by metal complexation.8
We have thus found the first stoichiometric reaction
where an alcohol is added to an alkyne-phosphino
fragment in a metallic complex in two steps: first to
give the (2-alkoxyvinyl)diphenylphosphino complex and
then to give the (2,2-dialkoxyethyl)diphenylphosphino
complex. The single addition of methanol to the ligand
is chemoselective (100% to the alkene in a first step)
and regioselective (100% anti-Markovnikov) but not
stereoselective (mixed cis-trans); the double addition
is chemoselective (100% to the alkane after 1 week) and
regioselective (100% anti-Markovnikov). The regiose-
lectivity could be associated with the steric hindrance
of the pentafluorophenyl-phosphinogold(III) unit, con-
sistent with the assignment of the trans isomer as the
main isomer.
Cr ysta l Str u ctu r e of Com p lex 3. The nature of the
gold(III) complex Au(C6F5)3(PPh2CH2CH(OMe)2) has
been confirmed by X-ray diffraction studies. To the best
of our knowledge, this is the first X-ray structure of a
coordination derivative containing this phosphine. The
molecular structure is shown in Figure 1, with selected
bonds and angles in Table 2. The gold(III) center
displays a slightly distorted square planar coordination
(mean deviation from best plane 0.10 Å) with CAuC and
(9) Bardaj´ı, M.; Laguna, A.; Orera, V. M.; Villacampa, M. D. Inorg.
Chem. 1998, 37, 5125.
(10) Uso´n, R.; Laguna, A.; Laguna, M.; Castilla, M. L.; J ones, P. G.;
Fittschen, C. J . Chem. Soc., Dalton Trans. 1987, 3017.
(11) Ferna´ndez, E. J .; Gimeno, M. G.; J ones, P. G.; Laguna, A.;
Laguna, M.; Lo´pez-de-Luzuriaga, J . M. Organometallics 1995, 14, 2918.
(12) Blanco, M. C.; Ferna´ndez, E. J .; J ones, P. G.; Laguna, A.; Lo´pez
de Luzuriaga, J . M.; Olmos, M. E. Angew. Chem., Int. Ed. Engl. 1998,
37, 3042.
(7) J ia, G.; Puddephatt, R. J .; Vittal, J . J . J . Organomet. Chem. 1993,
449, 211.
(8) (a) Fukuda, Y.; Utimoto, K. J . Org. Chem. 1991, 56, 3729. (b)
Teles, J . H.; Brode, S.; Chabanas, M. Angew. Chem., Int. Ed. Engl.
1998, 37, 1415. (c) Schmidbaur, H.; Herr, R.; Mu¨ller, G.; Riede, J .
Organometallics 1985, 4, 1208 and references therein.
(13) Ferna´ndez, E. J .; Gimeno, M. C.; J ones, P. G.; Laguna, A.; Lo´pez
de Luzuriaga, J . M.; Olmos, M. E. Chem. Ber. 1997, 130, 1513.
(14) Stein, J .; Fackler, J . P.; Paparizos, C.; Chen, H. W. J . Am. Chem.
Soc. 1981, 103, 2192.

An Acetylenephosphino Gold(III) Precursor
Organometallics, Vol. 20, No. 18, 2001 3909
Sch em e 2
in Au(C6F5)3{PPh(CH2PPh2)2} (2.356(2) Å);9 it is much
longer than that found in the related gold derivative
AuCl(iPr2PCCH) (2.222(2) Å), although this is an AuI-P
distance.
nances are transformed at -55 °C to a doublet of
doublets centered at 16.7 ppm because of the P-Ag
coupling. Finally, a resonance at 21.8 ppm is observed
for complex 8 from the PPN+ ion.
The FAB- mass spectra show the base peak at m/z
531 due to [Au(C6F5)2]-; additionally, a peak at m/z 2011
corresponding to [(F5C6)3Au(PPh2CC)Au(CCPPh2)Au-
(C6F5)3]- is observed for complexes 6-8. In the FAB+
mass spectra the parent peaks are observed at m/z 459
([Au(PPh3)]+), 1001 ([Au2(PPh2CC)(PPh2CH2CH2PPh2)]+)
and 369 ([Ag(PPh3)]+), respectively, for complexes 6, 7,
and 9; other significant peaks are observed as follows:
m/z (% abundance, assignment, complex) 1825 (2,
[(F5C6)3Au(PPh2CC)(AuPPh3)2]+, 6), 1407 (35, [Au3(PPh2-
CC)2(PPh2CH2CH2PPh2)]+, 7).
We have carried out the same reaction with the
previously reported7 gold(I) precursor AuCl(PPh2CCH),
but the dinuclear complex was not obtained (see eq 1);
a phosphine substitution reaction takes place, ac-
companied by the formation of the very stable acetyl-
idephosphino gold(I) polymer.
Syn th esis a n d Ch a r a cter iza tion of Acetylid e
Com p lexes. To prepare acetylide derivatives, we tried
a different approach. Instead of adding a base to the
reaction mixture, we carried out reactions by using
acetylacetonato (acac) derivatives of gold(I), silver(I), or
thallium(I) (in this case together with a chlorogold(I)
derivative) which are able to deprotonate an “acid” and
to coordinate to the resulting “base” the corresponding
gold(I) or silver(I) fragment (as result of the loss of the
acac ligand); this is known as the “acac method”.5 Thus,
we proceeded to react complex 1 with Au(acac)(PPh3),
Tl(acac) + AuCl(PPh3), Tl(acac) + (AuCl)2(µ-PPh2CH2-
CH2PPh2), [Au(acac)2](PPN) (PPN is PPh3dNdPPh3),
and Ag(acac)(PPh3), giving the corresponding di-, tri-,
or tetranuclear derivatives (see Scheme 2). Therefore,
we have succeeded in functionalizing the alkyne frag-
ment to produce alkynyl derivatives without any addi-
tion to the carbon-carbon triple bond.
Complexes 6-9 are air- and moisture-stable white
solids at room temperature. Their acetone solutions
behave as nonconducting for derivatives 6, 7, and 9 but
as 1:1 electrolytes for derivative 8. In the IR spectra the
absorption corresponding to CtCH disappeared but the
asymmetric CtC vibration is observed at 2082 (6), 2074
(7), 2052 (8), and 2049 and 2024 cm-1 (9), which
confirms that the carbon-carbon triple bond has not
reacted; all the spectra show absorptions corresponding
to the pentafluorophenyl rings around 965 and 800
AuClPh2PCtCH + Au(acac)PPh3 f
[Au(PPh2CC)]n + AuClPPh3 + Hacac (1)
Cr ysta l Str u ctu r e of Com p lex 6. The molecular
structure of the dinuclear gold(III)-gold(I) complex
(F5C6)3Au(PPh2CC)Au(PPh3) has been confirmed by
X-ray diffraction studies. The molecular structure is
shown in Figure 2, with selected bonds and angles in
Table 3. The gold(I) center shows an almost linear
geometry (175.7(2)°), which is connected with the linear
ethynylphosphine ligand (C2-C1-P ) 175.8(7)°) to give
a five-atom linear chain. The intramolecular gold-gold
distance is 6.069 Å, and the shortest intermolecular
gold-gold distance is 7.37 Å, which prevents any
metal-metal interactions, probably because of the steric
hindrance of the two bulky end groups of the molecule
(pentafluorophenyl and triphenylphosphine). The gold-
(III) center displays a square-planar coordination (mean
deviation from best plane 0.02 Å) with C-Au-C and
C-Au-P angles ranging from 88.5(3) to 91.56(19)°.
1
cm-1. The H NMR spectra show the disappearance of
the PCtCH doublet and display only phenyl resonances,
except for complex 7, where the methylene resonances
of the diphosphine are observed. The 19F NMR spectra
display only one type of tris(pentafluorophenyl)gold(III)
unit. The 31P{1H} NMR spectra show a singlet around
-6.6 ppm for complexes 6 and 7 or around -8.5 ppm
for complexes 8 and 9 due to the alkynylphosphino
gold(III) fragment and a singlet at about 40 ppm or a
broad resonance at 15.1 ppm for the phosphino gold(I)
or silver(I) fragment; the broad phosphino silver reso-

3910 Organometallics, Vol. 20, No. 18, 2001
Bardaj´ı et al.
Ta ble 4. Excita tion a n d Em ission Da ta in th e
Solid Sta te a t 77 K for Com p lexes 1-9
complex
λ
exc/nm
λemis/nm
1
2
3
4
5
6
7
8
9
334
300, 333
333
298, 343 (sh)
302, 330 (sh)
341
340, 386, 395
314
445, 457, 482
447, 458, 482, 517, 526
446
484
484, 517, 539
446
452, 458, 482 (sh)
483
while the excitation maximum is located at 340 nm with
a shoulder at 350 nm. The spectrum does not show any
vibrational fine structure, and it is the only derivative
able to possess short gold(I)-gold(I) distances (probably
intermolecular short distances as in (AuCCPh)2-
(µ-dppe));4b besides, the acetylenephosphine ligand is not
emissive in the solid state and therefore the nature of
the emission could be tentatively assigned to metal-
centered transitions.
However, complexes 2-9 luminesce at low tempera-
ture in the solid state, with excitation maxima in the
range 298-395 nm and emission maxima between 445
and 539 nm. The results are summarized in Table 4.
Complex 1 and the acetylenephosphine ligand are not
emissive under the same conditions. Exchanging meth-
oxide for ethoxide in complexes 2-5 leads to different
emission spectra, which indicates that this phosphine
ligand is involved in the electronic transitions. The
spectrum of complex 7 is similar to that found at room
temperature, except that the intensity has increased,
and it is clearly different from that observed for the
related complex 6, indicating the role of the possible
gold(I)-gold(I) contacts. The metal center attached to
the alkynyl fragment has a role in the luminescence
properties, and so the substitution of gold(I) by silver-
(I) leads to different spectra, as shown by comparison
of the spectra of complexes 6 and 9.
F igu r e 2. Molecular structure of complex 6, AuIII
-
(C6F5)3(PPh2CC)AuI(PPh3).
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 6
Au(1)-C(81)
Au(1)-C(71)
Au(1)-C(61)
Au(1)-P(1)
Au(2)-C(2)
Au(2)-P(2)
P(1)-C(1)
2.063(8)
2.067(8)
2.082(7)
2.3572(18)
1.982(8)
2.280(2)
1.733(8)
P(1)-C(11)
P(1)-C(21)
P(2)-C(51)
P(2)-C(41)
P(2)-C(31)
C(1)-C(2)
1.803(8)
1.804(8)
1.809(8)
1.815(8)
1.823(8)
1.220(11)
C(81)-Au(1)-C(71) 175.8(3)
C(11)-P(1)-Au(1) 113.1(2)
C(21)-P(1)-Au(1) 113.6(2)
C(51)-P(2)-C(41) 104.6(4)
C(81)-Au(1)-C(61)
C(71)-Au(1)-C(61)
C(81)-Au(1)-P(1)
C(71)-Au(1)-P(1)
C(61)-Au(1)-P(1)
C(2)-Au(2)-P(2)
C(1)-P(1)-C(11)
C(1)-P(1)-C(21)
C(11)-P(1)-C(21)
C(1)-P(1)-Au(1)
88.5(3)
88.5(3)
91.36(18) C(51)-P(2)-C(31) 107.1(4)
91.56(19) C(41)-P(2)-C(31) 105.0(3)
179.12(19) C(51)-P(2)-Au(2) 115.3(3)
175.7(2)
106.6(4)
105.9(4)
105.9(3)
111.3(3)
C(41)-P(2)-Au(2) 112.7(3)
C(31)-P(2)-Au(2) 111.4(2)
C(2)-C(1)-P(1)
C(1)-C(2)-Au(2)
175.8(7)
177.1(7)
The carbon-carbon bond triple distance is 1.220 (11)
Å, close to that found in AuCl(iPr2PCCH) (1.204(7) Å),7
and it is clearly different from the carbon-carbon single
bond distance found in complex 3 (1.509 (5) Å). The
P-Cacetylide bond distance is 1.733(8) Å, shorter than
found for the other P-C bond distances (from 1.803(8)
to 1.823(8) Å) or for the same bond in complex 3 (1.835
(4) Å). The AuIII-C bond distances trans to the phos-
phine and trans to pentafluorophenyl are insignificantly
different, taking account of the relatively high esd’s,
2.082(7) and 2.063(8)-2.067(8) Å, respectively, and
similar to those found for complex 3. The AuIII-P bond
distance is 2.3572(18) Å, shorter than in complex 3
(2.3692(8) Å) and similar to that reported in Au-
(C6F5)3{PPh(CH2PPh2)2} (2.356(2) Å).9 The AuI-P bond
distance is normal for these alkynyl derivatives (2.280-
(2) Å) but longer than in many gold(I) phosphino
complexes, as a consequence of the strong trans influ-
ence of the alkynyl group.4 The AuI-C bond distance is
1.982(8) Å, consistent with other reported gold(I) acetyl-
ide derivatives.3,4
Exp er im en ta l Section
Gen er a l Con sid er a tion s. All the reactions were carried
out under an argon atmosphere at room temperature. IR
spectra were recorded on a Perkin-Elmer 883 spectrophotom-
eter, over the range 4000-200 cm-1, by using Nujol mulls
between polyethylene sheets. 1H, 19F, and 31P{1H} NMR
spectra were recorded on a Bru¨ker ARX‚300 or GEMINI 2000
apparatus in CDCl3 solutions (if no other solvent is stated);
chemical shifts are quoted relative to SiMe4 (external, 1H),
CFCl3 (external, 19F), and 85% H3PO4 (external, 31P). C, H, N,
and S analyses were performed with a Perkin-Elmer 2400
microanalyzer. Conductivities were measured in acetone solu-
tion with a Philips PW 9509 apparatus. Mass spectra were
recorded on a VG Autospec using the FAB technique (with Cs
gun) and 3-nitrobenzyl alcohol as matrix. The luminescence
spectra were recorded on a Perkin-Elmer LS-50B spectrofluo-
rometer.
P r ep a r a tion of Au (C6F 5)3(P P h 2CCH) (1). To a 20 mL
diethyl ether solution of Au(C6F5)3(tht)15 (0.393 g, 0.5 mmol)
was added PPh2CCH7,16 (0.105 g, 0.5 mmol). After it was
stirred for 2 h, the solution was concentrated to ca. 2 mL and
the addition of petroleum ether afforded 1 as a white solid. A
second fraction was obtained by concentration and addition
P h otop h ysica l Stu d ies. Alkynyl gold(I) derivatives
often luminesce at room temperature, and the emission
has been associated with intraligand electronic transi-
tions, gold-centered transitions, Au-P to acetylide
transitions, or even gold-gold bond to acetylide transi-
tions.4a It is noteworthy that only derivative 7 is
luminescent at room temperature in the solid state, the
emission maxima being located at 445 and 455 nm,
(15) Uso´n, R.; Laguna, A.; Laguna, M. Inorg. Synth. 1989, 26, 87.
(16) Charrier, C.; Simonnin, M. P.; Chodkiewicz, W.; Cadiot, P. C.
R. Acad. Sci. Paris 1964, 258, 1537.

An Acetylenephosphino Gold(III) Precursor
Organometallics, Vol. 20, No. 18, 2001 3911
of more petroleum ether. Yield of 1: 381 mg, 84%. Data for 1:
1H NMR δ 3.51 (d, 3J (HP) ) 9.3 Hz, 1H, CH), 7.3-7.6 (m, 10H,
Ph). 19F NMR: δ -121.3 (m, 4Fo), -122.4 (m, 2Fo), -157.7 (t,
2Fp), -158.0 (t, 1Fp), -162.0 (m, 6Fm); 31P{1H} NMR δ -2.9
(s); IR 3209 (s, ν(CtCH)), 2071 (s, ν(CtC)), 967 (s, C6F5), 805
(s, C6F5), 796 (s, C6F5) cm-1. Anal. Calcd for C32H11AuF15P: C,
42.3; H, 1.2. Found: C, 41.9; H, 1.35. FAB- (m/z (%, assign-
ment)): 531 (100, [Au(C6F5)2]-), 907 (2, [M - H]-). FAB+ (m/z
(%, assignment)): 407 (100, [Au(PPh2CCH)]+), 617 (25, [Au-
(PPh2CCH)2]+), 951 (15, [Au(C6F5)2(PPh2CCH)2]+). Λ ) 4 Ω-1
) 5.4 Hz, 1H, CHCH2P), 7.4-7.6 (m, 10H, Ph); 19F NMR δ
-121.2 (m, 4Fo), -122.5 (m, 2Fo), -157.9 (t, 2Fp), -158.4 (t,
1Fp), -161.8 (m, 4Fm), -162.3 (m, 2Fm); 31P{1H} NMR δ 10.6
(m); IR 967 (s, C6F5), 795 (s, C6F5) cm-1. Anal. Calcd for C34H19
-
AuF15O2P: C, 42.0; H, 1.95. Found: C, 41.7; H, 2.25. FAB-
(m/z (%, assignment)): 531 (100, [Au(C6F5)2]-), 865 (35,
[Au(C6F5)4]-). FAB+ (m/z, (%, assignment)): 383 (100, [Au-
(PPh2H)]+), 471 (48, [Au(PPh2CH2CH(OMe)2)]+), 607 (78, [Au-
(C6F5)(PPh2CH2CHOMe)]+), 745 (4, [Au(PPh2CH2CH(OMe)2)2]+),
941 (3, [M-OMe]+). Λ ) 6 Ω-1 cm2 mol-1. Yield of 5: 70 mg,
70%. Data for 5: 1H NMR δ 0.96 (t, 3J (HH) ) 7.0 Hz, 6H, CH3-
CH2O), 2.89 (dd, 2J (HP) ) 9.6 Hz, 3J (HH) ) 5.5 Hz, 2H, CH2P),
3.11 (m, ABX3 system, 3J AX(HH) ) 7.0 Hz, 2J AB(HH) ) 9.5 Hz,
2H, CH3CH2O), 3.40 (m, ABX3 system, 3J BX(HH) ) 7.0 Hz, 2H,
CH3CH2O), 4.33 (“q”, 3J (HH) ) 3J (HP) ) 5.5 Hz, 1H, CHCH2P),
7.4-7.6 (m, 10H, Ph); 1H{31P} NMR 2.89 (d, 3J (HH) ) 5.5 Hz,
2H, CH2P), 4.33 (t, 1H, CHCH2P); 19F NMR δ -121.2 (m, 4Fo),
-122.5 (m, 2Fo), -157.9 (t, 2Fp), -158.4 (t, 1Fp), -161.7 (m,
4Fm), -162.3 (m, 2Fm); 31P{1H} NMR δ 11.4 (m). IR 965 (s,
C6F5), 795 (s, C6F5) cm-1. Anal. Calcd for C36H23AuF15O2P: C,
43.2; H, 2.3. Found: C, 43.4; H, 2.6. FAB- (m/z (%, assign-
ment)): 531 (100, [Au(C6F5)2]-), 698 (7, [Au(C6F5)4]-). FAB+
(m/z (%, assignment)): 383 (100, [Au(PPh2H)]+), 499 (37, [Au-
(PPh2CH2CH(OEt)2)]+), 621 (55, [Au(C6F5)(PPh2CH2CHOEt)]+).
cm2 mol-1
.
P r ep a r a tion of Au (C6F 5)3(P P h 2CHdCHOR) (R ) Me,
2a (tr a n s), 2b (cis); R ) Et, 4a (tr a n s), 4b (cis)). To Au-
(C6F5)3(PPh2CCH) (91 mg, 0.1 mmol) was added a 10 mL
methanol solution of NaOMe (6 mg, 0.1 mmol) or a 10 mL
ethanol solution of 0.01 M NaOH. After the mixture was
stirred for 2 h, the solvent was removed, dichloromethane was
added, and the solution was filtered through Celite then
concentrated to ca. 1 mL. Addition of petroleum ether afforded
complexes 2 and 4 as white solids which were washed with
petroleum ether. Yield of 2: 71 mg, 75%. Data for trans-2a :
1H NMR δ 3.84 (s, 3H, Me), 5.20 (dd, 2J (HP) ) 11.1 Hz, 3J (HH)
3
) 13.4 Hz, 1H, MeOCHdCHP), 6.90 (dd, J (HH) ) 13.4 Hz,
3J (HP) ) 10.6 Hz, 1H, MeOCHdCHP), 7.4-7.7 (m, 10H, Ph);
1H{31P} NMR δ 5.20 (d, 3J (HH) ) 13.4 Hz, 1H, MeOCHdCHP),
6.90 (d, 1H, MeOCHdCHP); 19F NMR δ -121.3 (m, 4Fo),
-122.6 (m, 2Fo), -158.2 (t, 2Fp), -158.4 (t, 1Fp), -162.0 (m,
4Fm), -162.3 (m, 2Fm); 31P{1H} NMR δ 9.0 (m). Data for cis-
Λ ) 2 Ω-1 cm2 mol-1
.
P r ep a r a tion of (F 5C6)3Au (P P h 2CC)Au (P P h 3) (6). This
complex can be prepared in two different ways. (a) To a 5 mL
dichloromethane solution of Au(C6F5)3(PPh2CCH) (45 mg, 0.05
mmol) was added Au(acac)(PPh3)17 (28 mg, 0.05 mmol), and
the mixture was stirred for about 1 h. The solution was
concentrated to ca. 1 mL, and the addition of petroleum ether
afforded 6 as a white solid. (b) To a 10 mL dichloromethane
solution of Au(C6F5)3(PPh2CCH) (45 mg, 0.05 mmol) was added
Tl(acac)18 (15 mg, 0.05 mmol), and the mixture was stirred
for about 2 h. Then AuCl(PPh3)19 (25 mg, 0.05 mmol) was
added. After the mixture was stirred for 1 h, TlCl was filtered
off and the clear solution concentrated to ca. 1 mL. Addition
of petroleum ether afforded 6 as a white solid. Yield of 6: 44
mg, 65%. Data for 6: 1H NMR δ 7.4-7.7 (m, Ph); 19F NMR δ
-120.9 (m, 4Fo), -121.9 (m, 2Fo), -159.0 (t, 1Fp), -159.3 (t,
2Fp), -162.8 (m, 6Fm); 31P{1H} NMR δ -6.7 (s, 1P, PPh2), 41.4
(s, 1P, PPh3); IR 2082 (s, ν(CtC)), 968 (s, C6F5), 810 (s, C6F5),
795 (s, C6F5) cm-1. Anal. Calcd for C50H25Au2F15P2: C, 43.95;
H, 1.85. Found: C, 44.3; H, 2.2. FAB- (m/z (%, assignment)):
531 (100, [Au(C6F5)2]-), 2011 (25, [(F5C6)3Au(PPh2CC)Au-
(CCPPh2)Au(C6F5)3]-). FAB+ (m/z (%, assignment)): 459 (100,
[Au(PPh3)]+), 721 (46, [Au(PPh3)2]+), 1825 (2, [M+Au(PPh3)]+).
2
2b: 1H NMR δ 4.01 (s, 3H, Me), 5.15 (“t”, J (HP) ) 3J (HH) )
6.9 Hz, 1H, MeOCHdCHP), 7.02 (dd, 3J (HH) ) 6.9 Hz, 3J (HP)
) 25.9 Hz, 1H, MeOCHdCHP), 7.4-7.7 (m, 10H, Ph); 1H{31P}
NMR δ 5.15 (d, 3J (HH) ) 6.9 Hz, 1H, MeOCHdCHP), 7.02 (d,
1H, MeOCHdCHP); 19F NMR δ -121.4 (m, 4Fo), -122.4 (m,
2Fo), -158.8 (t, 1Fp), -159.1 (t, 2Fp), -162.8 (m, 6Fm); 31P-
{1H} NMR δ -1.6 (m); IR 967 (s, C6F5), 795 (s, C6F5), 775 (sh,
C6F5) cm-1. Anal. Calcd for C33H15AuF15OP: C, 42.15; H, 1.6.
Found: C, 42.45; H, 1.7. FAB- (m/z (%, assignment)): 531 (100,
[Au(C6F5)2]-), 865 (35, [Au(C6F5)4]-). FAB+ (m/z (%, assign-
ment)): 439 (100, [Au(PPh2CHdCHOMe)]+). Λ ) 8 Ω-1 cm2
mol-1
.
Yield of 4: 67 mg, 70%. Data for trans-4a : 1H NMR δ 1.43
3
(t, J (HH) ) 7.1 Hz, 3H, CH3CH2O), 4.10 (q, 2H, CH3CH2O),
2
3
5.25 (dd, J (HP) ) 11.0 Hz, J (HH) ) 13.5 Hz, 1H, MeOCHd
3
CHP), 7.06 (dd, J (HP) ) 12.5 Hz, 1H, MeOCHdCHP), 7.4-
7.6 (m, 10H, Ph); H{31P} NMR δ 5.25 (d, J (HH) ) 13.5 Hz,
1H, MeOCHdCHP), 7.06 (d, 1H, MeOCHdCHP); 19F NMR δ
-121.3 (m, 4Fo), -122.6 (m, 2Fo), -158.3 (t, 2Fp), -158.4 (t,
1Fp), -162.0 (m, 4Fm), -162.3 (m, 2Fm); 31P{1H} NMR δ 8.5
1
3
Λ ) 4 Ω-1 cm2 mol-1
.
(m). Data for cis-4b: 1H NMR δ 1.15 (t, J (HH) ) 7.1 Hz, 3H,
3
P r ep a r a tion of [(F 5C6)3Au (P P h 2CC)Au (P P h 2CH2CH2-
P P h 2)Au (CCP P h 2)Au (C6F 5)3] (7). To a 10 mL dichlo-
romethane solution of Au(C6F5)3(PPh2CCH) (45 mg, 0.05 mmol)
was added Tl(acac) (15 mg, 0.05 mmol), and the mixture was
stirred for about 2 h. Then (AuCl)2(µ-PPh2CH2CH2PPh2)19 (22
mg, 0.025 mmol) was added. After this mixture was stirred
for 2 h, TlCl was filtered off and the clear solution concentrated
to ca. 1 mL. Addition of petroleum ether afforded 7 as an off-
white solid. Yield of 7: 55 mg, 85%. Data for 7: 1H NMR: δ
2.70 (s, 4H, CH2), 7.3-7.7 (m, 40H, Ph); 19F NMR δ -121.1
(m, 4Fo), -122.1 (m, 42Fo), -159.1(t, 1Fp), -159.2 (t, 2Fp),
-162.8 (m, 6Fm); 31P{1H} NMR δ -6.5 (s, 1P, PPh2), 39.0 (s,
1P, PPh2CH2); IR 2074 (s, ν(CtC)), 969 (s, C6F5), 797 (s, C6F5)
cm-1. Anal. Calcd for C90H44Au4F30P4: C, 41.45; H, 1.7.
Found: C, 41.8; H, 1.8. FAB- (m/z (%, assignment)): 531 (100,
[Au(C6F5)2]-), 2011 (10, [(F5C6)3Au(PPh2CC)Au(CCPPh2)Au-
(C6F5)3]-). FAB+ (m/z (%, assignment)): 1001 (100, [Au2(PPh2-
CH3CH2O), 3.99 (q, 2H, CH3CH2O), 5.10 (dd, 2J (HP) ) 12.7
3
3
Hz, J (HH) ) 7.1 Hz, 1H, MeOCHdCHP), 6.95 (dd, J (HP) )
18.6 Hz, 1H, MeOCHdCHP), 7.4-7.6 (m, 10H, Ph); H{31P}
1
NMR δ 5.10 (d, 3J (HH) ) 7.1 Hz, 1H, MeOCHdCHP), 6.95 (d,
1H, MeOCHdCHP); 19F NMR δ -121.1 (m, 4Fo), -122.3 (m,
2Fo), -158.8 (t, 1Fp), -159.0 (t, 2Fp), -162.7 (m, 6Fm); 31P-
{1H} NMR δ 1.1 (m); IR 968 (s, C6F5), 795 (s, C6F5) cm-1. Anal.
Calcd for C34H17AuF15OP: C, 42.8; H, 1.8. Found: C, 42.55;
H, 1.7. FAB- (m/z (%, assignment)): 531 (100, [Au(C6F5)2]-),
865 (4, [Au(C6F5)4]-). FAB+ (m/z (%, assignment)): 453 (100,
[Au(PPh2CHdCHOEt)]+). Λ ) 4 Ω-1 cm2 mol-1
.
P r ep a r a tion of Au (C6F 5)3(P P h 2CH2CH(OR)2) (R ) Me,
3; R ) Et, 5). To Au(C6F5)3(PPh2CCH) (91 mg, 0.1 mmol) was
added a 10 mL methanol solution of NaOMe (54 mg, 1 mmol)
or a 20 mL ethanol solution of 0.05 M NaOH. After the mixture
was stirred for 1 week, the solvent was removed, dichlo-
romethane was added, and the solution was filtered through
Celite and then concentrated to ca. 1 mL. Addition of petro-
leum ether afforded complexes 3 and 5 as white solids which
were washed with petroleum ether. Yield of 3: 84 mg, 86%.
(17) (a) Gibson, D.; J ohnson, B. F. G.; Lewis, J . J . Chem. Soc. A
1970, 367. (b) Vicente, J .; Chicote, M. T. Inorg. Synth. 1998, 32, 175.
(18) Vicente, J .; Chicote, M. T. Inorg. Synth. 1998, 32, 173.
(19) Schmidbaur, H.; Wohlleben, A.; Wagner, F.; Orama, O.; Hutt-
ner, G. Chem. Ber. 1977, 110, 1748.
2
3
Data for 3: 1H NMR δ 2.88 (dd, J (HP) ) 10.4 Hz, J (HH) )
5.4 Hz, 2H, CH2P), 3.11 (s, 6H, Me), 4.28 (“q”, 3J (HH) ) 3J (HP)

3912 Organometallics, Vol. 20, No. 18, 2001
Ta ble 5. Deta ils of Cr ysta l Da ta a n d Str u ctu r e Refin em en t for Com p lexes 3 a n d 6
Bardaj´ı et al.
3
6
empirical formula
fw
C
34H19AuF15O2P
C52H30Au2Cl3F15OP2
1517.98
972.43
temp/K
143
133
wavelength/Å
cryst syst
space group
a/Å
b/Å
c/Å
0.710 73
triclinic
P1h
0.710 73
monoclinic
P21/n
19.863(3)
13.2995(18)
19.928(3)
90
92.484(6)
90
5259.4(12)
4
10.5562(10)
10.5950(10)
15.7468(14)
109.378(3)
104.321(3)
91.630(3)
1598.0(3)
2
R/deg
â/deg
γ/deg
V/Å3
Z
density (calcd)/(Mg/m3)
abs coeff/mm-1
F(000)
2.021
4.775
936
1.917
5.877
2896
cryst habit
colorless square prism
colorless needle
0.50 × 0.10 × 0.05
1.42-28.29
cryst size/mm
θ range for data collecn/deg
index ranges
no. of rflns collected
indep rflns
0.31 × 0.14 × 0.13
1.42-30.03
-14 e h e 14, -14 e k e 14, -21 e l e 22
-26 e h e 26, -17 e k e 17, -26 e l e 26
28 899
79 626
9287 (R(int) ) 0.0387)
0.802, 0.611
9287/146/480
1.023
0.0299
0.0700
13044 (R(int) ) 0.0881)
0.928, 0.597
13 044/204/676
1.028
0.0519
0.1592
max, min transmission
no. of data/restraints/params
goodness of fit on F2
R1 (I > 2σ(I))a
wR2 (all data)b
largest diff peak, hole/(e Å-3
)
1.596, -2.842
3.044, -3.860
R1(F)) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) [∑{w(Fo - Fc2)2}/∑{w(Fo2)2}]0.5; w-1 ) σ2(Fo2) + (aP)2 + bP, where P ) [Fo + 2Fc2]/3 and a
a
b
2
2
and b are constants adjusted by the program.
CC)(PPh2CH2CH2PPh2)]+), 1407 (35, [Au3(PPh2CC)2(PPh2CH2-
was based on multiple scans (program SADABS). The struc-
tures were refined anisotropically on F2 (program SHELXL-
9721) using a system of restraints (to light atom U values and
local ring symmetry). H atoms were included using a riding
model. The structure refinement of 6 involved a region of badly
resolved residual electron density, tentatively identified as one
chloroform molecule and one methanol molecule, the last of
which has been idealized using three different sites. However,
this should be interpreted with caution.
CH2PPh2)]+). Λ ) 9 Ω-1 cm2 mol-1
.
P r ep a r a t ion of [(F 5C6)3Au (P P h 2CC)Au (CCP P h 2)Au -
(C6F 5)3][P P N] (8). To a 15 mL dichloromethane solution of
Au(C6F5)3(PPh2CCH) (91 mg, 0.1 mmol) was added [Au(acac)2]-
[PPN]20 (47 mg, 0.05 mmol), and the mixture was stirred for
about 4 h. The solvent was removed and the white residue
washed with petroleum ether. Yield of 8: 89 mg, 70%. Data
for 8: 1H NMR δ 7.3-7.7 (m, Ph); 19F NMR δ -121.3 (m, 6Fo),
-159.6 (t, 2Fp), -159.7 (t, 1Fp), -163.0 (m, 6Fm); 31P{1H} NMR
δ -8.6 (s, 1P, PPh2), 21.8 (s, 1P, PPh3); IR 2052 (s, ν(CtC)),
Con clu sion s
966 (s, C6F5), 794 (s, C6F5) cm-1. Anal. Calcd for C100H50Au3F30
-
We have carried out reactions of the acetylenephos-
phine ligand coordinated to the gold(III) complex 1 in
two completely different ways. On one hand, we have
carried out single or double anti-Markovnikov alcohol
additions to the acetylene fragment to obtain (2-alkox-
yvinyl)diphenylphosphine or (2,2-dialkoxyethyl)diphen-
ylphosphine ligands. On the other hand, we have
prepared di-, tri-, or tetranuclear alkynylphosphino
complexes with gold(I), silver(I), and gold(III) centers.
NP4: C, 47.1; H, 2.0; N, 0.55. Found: C, 47.45; H, 2.3; N, 0.6.
FAB- (m/z (%, assignment)): 531 (100, [Au(C6F5)2]-), 865 (3,
[Au(C6F5)4]-), 2011 (2, [M - PPN]-). Λ ) 100 Ω-1 cm2 mol-1
.
P r ep a r a tion of (F 5C6)3Au (P P h 2CC)Ag(P P h 3) (9). To a
5 mL dichloromethane solution of Au(C6F5)3(PPh2CCH) (45 mg,
0.05 mmol) was added Ag(acac)(PPh3)17a (24 mg, 0.05 mmol)
and the mixture stirred for about 3 h, protected from light.
The solvent was removed and the white residue washed with
petroleum ether. Yield of 9: 43 mg, 68%. Data for 9: 1H NMR
δ 7.4-7.7 (m, Ph); 19F NMR δ -120.9 (m, 4Fo), -121.9 (m, 2Fo),
-159.1 (t, 1Fp), -159.3 (t, 2Fp), -162.7 (m, 2Fm), -163.0 (m,
4Fm); 31P{1H} NMR δ -8.4 (s, 1P, PPh2), 15.1 (br s, 1P, PPh3);
31P{1H} NMR (-55 °C) δ -8.5 (s, 1P, PPh2), 16.7 (dd,
1J (105,107AgP) ) 486.3 and 556.0 Hz, 1P, PPh3); IR 2049 (s,
Ack n ow led gm en t. We thank the Direccio´n General
de Investigacio´n Cient´ıfica y Te´cnica (Project PB97-
1010-C02-01) and the Fonds der Chemischen Industrie
for financial support. We also thank Dr. J . Galba´n
(Universidad de Zaragoza, Zaragoza, Spain) for kindly
providing apparatus facilities.
ν(CtC)), 2024 (s, ν(CtC)), 967 (s, C6F5), 794 (s, C6F5) cm-1
.
Anal. Calcd for C50H25AgAuF15P2: C, 47.0; H, 1.95. Found: C,
47.4;H, 2.2. FAB- (m/z(%, assignment)): 531 (100, [Au(C6F5)2]-),
865 (8, [Au(C6F5)4]-). FAB+ (m/z (%, assignment)): 369 (100,
[Ag(PPh3)]+), 631 (45, [Ag(PPh3)2]+). Λ ) 12 Ω-1 cm2 mol-1
.
Su p p or tin g In for m a tion Ava ila ble: X-ray crystallo-
graphic data for the structure determination of complexes 3
and 6. This material is available free of charge via the Internet
at http://pubs.acs.org.
Cr ysta l Str u ctu r e Deter m in a tion of 3 a n d 6. Crystal
data and details of the data collection and structure refinement
of Au(C6F5)3(PPh2CH2CH(OMe)2) and (F5C6)3Au(PPh2CC)Au-
(PPh3) are given in Table 5. Data were measured on a Bruker
SMART 1000 CCD diffractometer. An absorption correction
OM010385+
(20) Vicente, J .; Chicote, M. T.; Saura-Llamas, I.; Lagunas, M. C.
Chem. Commun. 1992, 915.
(21) Sheldrick, G. M. SHELXL 97: A Program for Crystal Structure
Refinement; University of Go¨ttingen: Go¨ttingen, Germany, 1997.