Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I) centers

Article abstract of DOI:10.1021/ic0100875

The monohapto neutral 2-(diphenylphosphino)aniline PNH₂ complexes [Au(C₆F₅)₂X(PNH₂)] (X = C₆F₅(1), Cl(2)) have been obtained from [Au(C₆F₅)₃(tht)] or Au(C₆F₅)₂ and PNH₂, and the cationic [Au(C₆F₅)_2- (PNH₂)]ClO₄ (3) has been similarly prepared from [Au(C₆F₅)₂(OEt₂)₂] ClO₄ and PNH₂ or from 2 and AgClO₄. The neutral amido complex [Au(C₆F₅)₂(PNH)] (4) can be obtained by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO₃)(PPh₃)] or [Au(OClO₃)(PPh₃)] to give the dinuclear species [Au(C₆F₅)₂{PNH(MPPh₃)}] ClO₄ (M = Ag (5), Au (6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh₃)]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C₆F₅)₂{PN(AuPPh₃}] ClO₄ (7) is obtained. The crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)-Au(III) interaction.

Full text of DOI:10.1021/ic0100875

3018
Inorg. Chem. 2001, 40, 3018-3024
Ability of a Au(III)-N Unit to Bond Two Aurophilically Interacting Gold(I) Centers†
Eduardo J. Ferna´ndez, Manuel Gil, and M. Elena Olmos
Departamento de Qu´ımica, Universidad de La Rioja, Grupo de S´ıntesis Qu´ımica de La Rioja,
UA-CSIC, Madre de Dios 51, E-26006 Logron˜o, Spain
Olga Crespo and Antonio Laguna*
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
Peter G. Jones
Institu¨t fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t, Postfach 3329,
D-38023 Braunschweig, Germany
ReceiVed January 23, 2001
The monohapto neutral 2-(diphenylphosphino)aniline (PNH2) complexes [Au(C6F5)2X(PNH2)] (X ) C6F5 (1), Cl
(2)) have been obtained from [Au(C6F5)3(tht)] or [Au(C6F5)2(µ-Cl)]2 and PNH2, and the cationic [Au(C6F5)2-
(PNH2)]ClO4 (3) has been similarly prepared from [Au(C6F5)2(OEt2)2]ClO4 and PNH2 or from 2 and AgClO4.
The neutral amido complex [Au(C6F5)2(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac
) acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO3)(PPh3)] or
[Au(OClO3)(PPh3)] to give the dinuclear species [Au(C6F5)2{PNH(MPPh3)}]ClO4 (M ) Ag (5), Au (6)). The
latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh3)]; when the molar ratio of
the same reagents is 1:2, the trinuclear cationic complex [Au(C6F5)2{PN(AuPPh3)2}]ClO4 (7) is obtained. The
crystal structures of complexes 2-4 and 7 have been established by X-ray crystallography; the last-mentioned
displays an unusual Au(I)-Au(III) interaction.
Introduction
11 metal complexes of PNH2 have been reported12 and the only
oxidation state represented is +1, with the exception of the Cu-
(II) derivative [Cu(PNH2)2](BF4)2.12d
Polyfunctional ligands with P-, S-, or N-donor centers are
often instrumental in the preparation of a variety of polynuclear
complexes. In the case of gold, these complexes may be used
for a number of applications, including chemotherapy, diag-
nostics, electron microscopy, catalysis, and surface technology.1-5
One such ligand is the P,N-donor 2-(diphenylphosphino)aniline
(PNH2), which has been employed for the synthesis of a number
of derivatives of W, Ni, Pd, Pt, Rh, Os, and Re in which it
usually acts as bidentate chelating ligand and the nitrogen center
is sometimes deprotonated.6-11 In contrast, only a few group
There is a general acceptance of the relativistic effects
exhibited by the elements of the third transition series.13 These
effects reach a maximum at gold, and the topic has recently
been reviewed in terms of theoretical and experimental evi-
dence,14 although the theoretical understanding of such interac-
tions still remains in a preliminary state.15 A strong attractive
and energetically favorable interaction has been observed
between gold(I) atoms (d10 configuration) in numerous poly-
nuclear gold compounds,16-21 while gold(I)-gold(III) interac-
† Dedicated to Prof. R. Uso´n on the occasion of his 75th birthday.
(1) Rapson, W. S.; Groenewald, T. In Gold Usage; Academic Press:
London, 1978.
(10) Adams, C. J.; Bruce, M. I.; Duckworth, P. A.; Humphrey, P. A.; Kuhl,
O.; Tiekink, E. R. T.; Cullen, W. R.; Braunstein, P.; Cea, S. C.;
Skelton, B. W.; White, A. H. J. Organomet. Chem. 1994, 467, 251.
(11) Bolzati, C.; Tisato, F.; Refosco, F.; Bandoli, G.; Dolmella, A. Inorg.
Chem. 1996, 35, 6221.
(12) (a) Lo´pez-de-Luzuriaga, J. M.; Schier, A.; Schmidbaur, H. Chem. Ber.
1997, 130, 647. (b) Papathanasiou, P.; Salem, G.; Waring, P.; Willis,
C. J. Chem. Soc., Dalton Trans. 1997, 3435. (c) Crociani, L.;
Anacardio, R.; Traldi, P.; Corain, B. Inorg. Chim. Acta 1998, 282,
119. (d) Tisato, F.; Pilloni, G.; Refosco, F.; Bandolli, G.; Corvaja, C.;
Corain, B. Inorg. Chim. Acta 1998, 275-276, 401. (e) Tiekink, E. R.
T. J. Coord. Chem. 1993, 28, 233. (f) Shaw, B. L.; Iranpoor, N.; Perera,
S. D.; Thornton-Pett, M.; Vessey, J. D. J. Chem. Soc., Dalton Trans.
1998, 1885. (g) Slavin, A. M. Z.; Smith, M. B. New J. Chem. 1999,
23, 777.
(13) Kaltsoyannis, N. J. Chem. Soc., Dalton Trans. 1997, 1.
(14) Pyykko¨, P. Chem. ReV. 1988, 88, 563.
(15) Pyykko¨, P. Chem. ReV. 1997, 97, 597.
(16) Schmidbaur, H. Interdiscip. Sci. ReV. 1992, 17, 213.
(17) Schmidbaur, H. Pure Appl. Chem. 1993, 65, 691.
(18) Yang, Y.; Ramamoorthy, V.; Sharp, P. R. Inorg. Chem. 1993, 32,
1946.
(2) Sadler, P. J. Gold Bull. 1976, 9, 110.
(3) Dash, K. C.; Schmidbaur, H. In Metal Ions in Biological Systems;
Sigel, H., Ed.; Marcel Dekker: New York/Basel, 1982; Vol. 14, p
179 ff.
(4) Ulman, A. Chem. ReV. 1996, 96, 1533 and references therein.
(5) Shaw, C. F., III In Gold: Progress in Chemistry, Biochemistry and
Technology; Schmidbaur, H., Ed.; Wiley: New York, 1999; p 259 ff.
(6) (a) Pietsch, J.; Wolski, A.; Dahlenburg, L.; Moll, M.; Berke, H.;
Veghini, D.; Eremenko, I. L. J. Organomet. Chem. 1994, 472, 55. (b)
Redshaw, C.; Gibson, V. C.; Clegg, W.; Edwards, A. J.; Miles, B. J.
Chem. Soc., Dalton Trans. 1997, 3343.
(7) Crociani, L.; Tisato, F.; Refosco, F.; Bandoli, G.; Corain, B. Eur. J.
Inorg. Chem. 1998, 1689.
(8) (a) Casellato, U.; Guerriero, P.; Tamburini, S.; Vigato, P. A. Inorg.
Chim. Acta 1997, 260, 1. (b) Chatterjee, S.; Hockless, D. C. R.; Salem,
G.; Waring, P. J. Chem. Soc., Dalton Trans. 1997, 3889.
(9) (a) Organ, G. J.; Cooper, M. K.; Henrick, K.; McPartlin, M. J. Chem.
Soc., Dalton Trans. 1984, 2377. (b) Cooper, M. K.; Organ, G. J.;
Duckworth, P. A.; Henrick, K.; McPartlin, M. J. Chem. Soc., Dalton
Trans. 1988, 2287.
(19) Jones, P. G. Gold Bull. 1981, 14, 102; 1983, 16, 114; 1986, 19, 46.
10.1021/ic0100875 CCC: $20.00 © 2001 American Chemical Society
Published on Web 05/19/2001

[Au(C6F5)2X(PNH2)] Complexes
Inorganic Chemistry, Vol. 40, No. 13, 2001 3019
g) or [Au(C6F5)2(µ-Cl)]2 (0.1 mmol, 0.11 g) was added PNH2 (0.2 mmol,
0.06 g). After 30 min of stirring the solution was concentrated to ca.
5 mL and addition of hexane (20 mL) precipitated complexes 1 or 2
as white solids. Yield: 73 (1), 85% (2). ΛM: 3 (1), 3 (2) Ω-1 cm2
mol-1. FAB/MS: [M]+ at m/z ) 975 (3%, 1). Anal. Calcd for C36H16-
AuF15NP (1): C, 44.35; H, 1.65; N, 1.45. Found: C, 43.8; H, 1.6; N,
1.4. Calcd for C30H16AuClF10NP (2): C, 42.7; H, 1.9: N, 1.65.
Found: C, 42.85; H, 2.25; N, 1.95. 31P{1H} NMR (CDCl3), δ: (1)
12.0 (m); (2) 20.7 (m). 19F NMR (CDCl3), δ: (1) -119.9 (m, 4F, Fm),
-157.1 [t, 2F, 3J(Fm-Fp) ) 19.8 Hz, Fp], -161.0 (m, 4F, Fo), -121.9
(m, 2F, Fm), -157.5 [t, 1F, 3J(Fm-Fp) ) 19.9 Hz, Fp], -161.3 (m, 2F,
Fo); (2) -121.6 (m, 2F, Fm), -156.8 [t, 1F, 3J(Fm-Fp) ) 19.9 Hz, Fp],
tions have only been previously described in mixed-valence
doubly bridged ylide systems where the gold centers are forced
to be in close proximity,22-25 in the polynuclear sulfur-centered
complex [{S(AuI2dppf)}2{AuIII(C6F5)}]OTf (dppf ) 1,1′-bis-
(diphenylphosphino)ferrocene),26 and in the derivative [AuIAuIII-
Me2(PMe3)2(C4F6)].27 It is notable that, apart from these, not
too many interactions have been observed in other d8-d10
systems.28
Taking these facts into account, we have centered our interest
on the study of gold(III) derivatives of 2-(diphenylphosphino)-
aniline and their reactivity toward Au(I) or Ag(I) species in order
to establish whether they display unusual new metal-metal
interactions.
3
-160.4 (m, 2F, Fo), -122.9 (m, 2F, Fm), -156.8 [t, 1F, J(Fm-Fp) )
19.9 Hz, Fp], -161.1 (m, 2F, Fo). 1H NMR (CDCl3), δ: (1) 7.58-6.64
(m, 14H, aromatic protons), 3.8 (m, 2H, NH2); (2) 7.72-6.67 (m, 14H,
aromatic protons), 3.9 (m, 2H, NH2).
Synthesis of [Au(C6F5)2(PNH2)]ClO4 (3). This complex was
obtained by two methods.
Experimental Section
Reagents. AgClO4 was purchased from Aldrich and used as received.
The compounds PNH2,29 [Au(C6F5)3(tht)],30 [Au(C6F5)2(µ-Cl)]2,31 [Au-
(C6F5)2(OEt2)2]ClO4,32 [Au(C6F5)2(acac)],31 Tl(acac),33 PPN(acac),34
[Ag(OClO3)(PPh3)],35 and [Au(acac)(PPh3)]36 were prepared by litera-
ture methods.
Caution! Perchlorate salts with organic cations may be explosive.
Apparatus. Infrared spectra were recorded in the range 4000-200
cm-1 on a Perkin-Elmer 883 spectrophotometer and on a Perkin-Elmer
FT-IR Spectrum 1000 spectrophotometer using Nujol mulls between
Method a. To a freshly prepared solution of [Au(C6F5)2(OEt2)2]ClO4
(0.2 mmol) was added PNH2 (0.2 mmol, 0.06 g), whereupon a white
solid started to form. The mixture was stirred for 2 h to complete the
precipitation of 3, which was filtered off and washed with diethyl ether.
Yield: 90%.
Method b. To an acetone solution of 2 (0.2 mmol, 0.17 g) was added
AgClO4 (0.2 mmol, 0.04 g). After stirring of the solution for 2 h, the
AgCl formed was filtered off, the resulting solution concentrated in
vacuo, and 20 mL of diethyl ether was added to precipitate 3 as a white
solid. Yield: 85%. ΛM: 78 Ω-1 cm2 mol-1. FAB/MS: [M]+ at m/z )
808 (87%). Anal. Calcd for C30H16AuClF10NO4P: C, 39.7; H, 1.8; N,
1.55. Found: C, 40.15; H, 1.45; N, 1.45. 31P{1H} NMR (CDCl3), δ:
45.1 (m). 19F NMR (CDCl3), δ: -121.3 (m, 2F, Fm), -154.1 [t, 1F,
3J(Fm-Fp) ) 19.9 Hz, Fp], -159.8 (m, 2F, Fo), -122.0 (m, 2F, Fm),
-154.6 [t, 1F, 3J(Fm-Fp) ) 20.1 Hz, Fp], -160.0 (m, 2F, Fo). 1H NMR
(CDCl3), δ: 8.03-7.51 (m, 14H, aromatic protons).
polyethylene sheets. Conductivities were measured in ca. 5 × 10-4
M
acetone solutions with a Jenway 4010 conductimeter. C, H, and N
analyses were carried out with a Perkin-Elmer 240C microanalyzer.
Mass spectra were recorded on a VG Autospec using FAB techniques
and nitrobenzyl alcohol as matrix and on a HP59987 A Electrospray.
1H, 19F, and 31P{1H} NMR spectra were recorded on a Bruker ARX
300 in CDCl3 solutions. Chemical shifts are quoted relative to SiMe4
(1H, external), CFCl3 (19F, external), and H3PO4 (85%) (31P, external).
Synthesis of [Au(C6F5)2X(PNH2)] (X ) C6F5 (1), Cl (2)). To a
dichloromethane solution (20 mL) of [Au(C6F5)3(tht)] (0.2 mmol, 0.16
Synthesis of [Au(C6F5)2(PNH)] (4). This complex was obtained by
three methods.
Method a. To a solution of [Au(C6F5)2(acac)] (0.2 mmol, 0.13 g)
in 20 mL of dichloromethane under a nitrogen atmosphere was added
PNH2 (0.2 mmol, 0.06 g); the solution immediately turned yellow. After
30 min of stirring it was concentrated to ca. 5 mL and hexane (20 mL)
was added to precipitate 4 as a yellow solid. Yield: 36%.
Method b. To a dichloromethane solution of 2 (0.2 mmol, 0.17 g)
under a nitrogen atmosphere was added Tl(acac) (0.2 mmol, 0.06 g).
The mixture was stirred for 3 h, and the TlCl formed was filtered off
over Celite. The resulting yellow solution was concentrated in vacuo,
and 20 mL of hexane was added to precipitate 4 as a yellow solid.
Yield: 54%.
Method c. To a solution of 3 (0.2 mmol, 0.18 g) in 20 mL of
dichloromethane under a nitrogen atmosphere was added PPN(acac)
(0.2 mmol, 0.13 g); the solution immediately turned yellow. After being
stirred for 30 min, the solution was evaporated and diethyl ether was
added to precipitate the PPNClO4 formed, which was filtered off over
Celite. The resulting yellow solution was concentrated in vacuo, and
20 mL of hexane was added to precipitate 4 as a yellow solid. Yield:
57%. ΛM: 2 Ω-1 cm2 mol-1. FAB/MS: [M]+ at m/z ) 807 (100%).
Anal. Calcd for C30H15AuF10NP: C, 44.65; H, 1.85; N, 1.75. Found:
C, 45.0; H, 2.0; N, 1.7. 31P{1H} NMR (CDCl3), δ: 39.5 (m). 19F NMR
(CDCl3), δ: -121.3 (m, 2F, Fm), -156.8 [t, 1F, 3J(Fm-Fp) ) 19.7 Hz,
Fp], -161.1 (m, 2F, Fo), -121.5 (m, 2F, Fm), -157.0 [t, 1F, 3J(Fm-Fp)
) 19.9 Hz, Fp], -161.7 (m, 2F, Fo). 1H NMR (CDCl3), δ: 7.60-6.44
(m, 14H, aromatic protons), 5.19 (s, 1H, NH).
Synthesis of [Au(C6F5)2{PNH(AgPPh3)}]ClO4 (5). To a solution
of 4 (0.2 mmol, 0.16 g) in dichloromethane under nitrogen atmosphere
was added [Ag(OClO3)(PPh3)] (0.2 mmol, 0.09 g). After 30 min of
stirring the solution was concentrated in vacuo to ca. 5 mL, and addition
of diethyl ether (20 mL) precipitated complex 5 as a yellow solid.
Yield: 25%. ΛM: 83 Ω-1 cm2 mol-1. ES/MS: [M]+ at m/z ) 1177
(7%). Anal. Calcd for: C48H30AgAuClF10NO4P2: C, 45.15; H, 2.35;
N, 1.1. Found: C, 45.45; H, 2.5; N, 1.05. 31P{1H} NMR (HDA, 298
K), δ: 45.2 (m, 1P, PPh2), 14.1 (dm, 1P, AgPPh3). 31P{1H} NMR
(HDA, 223 K), δ: 45.6 (m, 1P, PPh2), 13.0 [dd, 1P, J(109Ag-P) )
(20) Schmidbaur, H. Chem. Soc. ReV. 1995, 391.
(21) Ferna´ndez, E. J.; Lo´pez de Luzuriaga, J. M.; Monge, M. Rodr´ıguez,
M. A.; Crespo, O.; Gimeno, M. C.; Laguna, A.; Jones, P. G. Inorg.
Chem. 1998, 37, 6002.
(22) Mazany, A. M.; Fackler, J. P., Jr. J. Am. Chem. Soc. 1984, 106, 801.
(23) Fackler, J. P., Jr.; Trzcinska-Bancroft, B. Organometallics 1985, 4,
1891.
(24) Raptis, R. G.; Porter, L. C.; Emrich, R. J.; Murray, H. H.; Fackler, J.
P., Jr. Inorg. Chem. 1990, 29, 4408.
(25) Schmidbaur, H.; Hartmann, C.; Reber, G.; Mu¨ller, G. Angew. Chem.,
Int. Ed. Engl. 1987, 26, 1146.
(26) Calhorda, M. J.; Canales, F.; Gimeno, M. C.; Jime´nez, J.; Jones, P.
G.; Laguna, A.; Veiros, L. F. Organometallics 1997, 16, 3837.
(27) Jarvis, J. A. J.; Johnson, A.; Puddephatt, R. J. J. Chem. Soc., Chem.
Commun. 1973, 373.
(28) (a) Crespo, O.; Laguna, A.; Ferna´ndez, E. J.; Lo´pez de Luzuriaga, J.
M.; Jones, P. G.; Teichert, M.; Monge, M.; Pyykko¨, P.; Runeberg,
N.; Schu¨tz, M.; Werner, H.-J. Inorg. Chem. 2000, 39, 4786 and
references therein. (b) Bennett, M. A.; Contel, M.; Hockless, D. C.
R.; Welling, L. L . Chem. Commun. 1998, 2401. (c) Krumm, M.;
Zangrando, E.; Randaccio, L.; Menzer, S.; Danzmann, A.; Holthenrich,
D.; Lippert, B. Inorg. Chem. 1993, 32, 2183. (d) Van der Ploeg, A. F.
M. I.; Van Koten, G.; Vrieze, K.; Spek, A. L.; Duisenberg, A. J. M.
Organometallics 1982, 1, 1066.
(29) Cooper, M. K.; Downes, J. M.; Duckworth, P. A.; Kerby, M. C.;
Powell, R. J.; Soucek, M. D. Inorg. Synth. 1989, 25, 129.
(30) Uso´n, R.; Laguna, A.; Laguna, M.; Ferna´ndez, E.; Jones, P. G.;
Sheldrick, G. M. J. Chem. Soc., Dalton Trans. 1982, 1971.
(31) Uso´n, R.; Laguna, A.; Laguna, M.; Abad, M. J. Organomet. Chem.
1983, 249, 437.
(32) Uso´n, R.; Laguna, A.; Arrese, M. L. Synth. React. Inorg. Met.-Org.
Chem. 1984, 14, 557.
(33) Lee, A. G. In The Chemistry of Thallium; Elsevier: Amsterdam, 1971;
p 271.
(34) Ferna´ndez, E. J.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Laguna,
M.; Lo´pez de Luzuriaga, J. M. J. Chem. Soc., Dalton Trans. 1992,
3365.
(35) Cotton, F. A.; Falvello, L. R.; Uso´n, R.; Fornie´s, J, Toma´s, M.; Casas,
J..M.; Ara, I. Inorg. Chem. 1987, 26, 1366.
(36) Gibson, D.; Johnson, B. F. G.; Lewis, J. J. Chem. Soc. A 1970, 367.

3020 Inorganic Chemistry, Vol. 40, No. 13, 2001
Ferna´ndez et al.
803 Hz, J(107Ag-P) ) 691 Hz, AgPPh3]. 19F NMR (HDA), δ: -121.0
(m, 2F, Fm), -158.2 [t, 1F, 3J(Fm-Fp) ) 19.9 Hz, Fp], -162.6 (m, 2F,
Table 1. Details of Data Collection and Structure Refinement for
Complexes 2 and 3
3
Fo), -121.7 (m, 2F, Fm), -158.9 [t, 1F, J(Fm-Fp) ) 19.9 Hz, Fp],
compd
-162.7 (m, 2F, Fo). 1H NMR (HDA), δ: 7.79-6.52 (m, 14H, aromatic
protons).
2
3
chem formula
cryst habit
cryst size/mm
cryst system
space group
a/Å
C30H16AuClF10NP
colorless trapezoid
0.40 × 0.40 × 0.30
triclinic
P1h
C31.5H19AuCl4F10NO4P
colorless prism
0.36 × 0.18 × 0.10
triclinic
P1h
9.241(2)
13.752(2)
15.6517(10)
100.404(10)
102.338(10)
101.282(10)
1853.5(5)
2
Synthesis of [Au(C6F5)2{PNH(AuPPh3)}]ClO4 (6). This complex
was obtained by two methods.
Method a. To a solution of 4 (0.2 mmol, 0.16 g) in THF under
nitrogen atmosphere was added a freshly prepared solution of [Au-
(OClO3)PPh3] (0.2 mmol) (obtained by addition of the equimolecular
amount of AgClO4 to a THF solution of [AuCl(PPh3)] under nitrogen
at 0 °C). After 30 min of stirring the solution was concentrated in vacuo
to ca. 5 mL, and addition of diethyl ether (20 mL) precipitated complex
6 as an orange solid. Yield: 42%.
Method b. To a solution of 3 (0.2 mmol, 0.18 g) in 20 mL of
dichloromethane under a nitrogen atmosphere was added [Au(acac)-
(PPh3)] (0.2 mmol, 0.11 g); the solution turned orange. After 30 min
of stirring the solution was concentrated to ca. 5 mL, and diethyl ether
added to precipitate 6 as an orange solid. Yield: 47%. ΛM: 86 Ω-1
cm2 mol-1. ES/MS: [M]+ at m/z ) 1266 (95%). Anal. Calcd for C48H30-
Au2ClF10NO4P2: C, 42.2; H, 2.2; N, 1.05. Found: C, 42.45; H, 2.3; N,
1.4. 31P{1H} NMR (CDCl3), δ: 42.4 (m, 1P, PPh2), 29.3 (s, 1P,
AuPPh3). 19F NMR (CDCl3), δ: -121.3 (m, 2F, Fm), -155.0 [t, 2F,
3J(Fm-Fp) ) 19.7 Hz, Fp], -159.8 (m, 2F, Fo), -121.6 (m, 2F, Fm),
-155.1 [t, 1F, 3J(Fm-Fp) ) 19.7 Hz, Fp], -160.9 (m, 2F, Fo). 1H NMR
(CDCl3), δ: 8.05-7.07 (m, 14H, aromatic protons).
9.8992(8)
11.828(2)
13.672(2)
110.194(16)
97.087(14)
106.108(12)
1400.1(4)
2
b/Å
c/Å
R/deg
â/deg
γ/deg
V/Å3
Z
Dc/g cm-3
M
2.002
1.855
1035.21
998
843.82
F(000)
T/°C
2θmax/deg
µ(Μo KR)/mm-1
Transm
808
-100
-100
50
56
5.497
4.387
0.979, 0.522
4975
0.999, 0.589
12 666
no. of reflcns measd
no. of unique reflcns
Rint
4759
8884
0.0199
0.0383
Ra (F > 4σ(F))
wRb (F2, all reflcns)
no. of reflcns used
no. of params
No. of restraints
Sc
0.0225
0.0498
0.0536
0.1244
4759
403
374
1.036
0.979
8884
457
129
0.996
1.742
Synthesis of [Au(C6F5)2{PN(AuPPh3)2}]ClO4 (7). This complex
was obtained by two methods.
Method a. To a solution of 3 (0.1 mmol, 0.09 g) in 20 mL of
dichloromethane under a nitrogen atmosphere was added [Au(acac)-
(PPh3)] (0.2 mmol, 0.11 g); the solution became yellow. After 30 min
of stirring the solution was concentrated in vacuo, and addition of 20
mL of diethyl ether precipitated 7 as a yellow solid. Yield: 50%.
Method b. To a dichloromethane solution of 6 (0.1 mmol, 0.14 g)
under a nitrogen atmosphere was added [Au(acac)(PPh3)] (0.1 mmol,
0.06 g); the solution turned yellow. After 30 min of stirring the solution
was concentrated to ca. 5 mL, and diethyl ether was added to precipitate
7 as a yellow solid. Yield: 37%. ΛM: 79 Ω-1 cm2 mol-1. ES/MS:
[M]+ at m/z ) 1725 (16%). Anal. Calcd for C66H45Au3ClF10NO4P3: C,
43.45; H, 2.45; N, 0.8. Found: C, 43.8; H, 2.7; N, 1.0. 31P{1H} NMR
(CDCl3), δ: 46.3 (m, 1P, PPh2), 27.5 (s, 2P, AuPPh3). 19F NMR
(CDCl3), δ: -116.2 (m, 2F, Fm), -153.7 [t, 2F, 3J(Fm-Fp) ) 20.4 Hz,
Fp], -159.2 (m, 2F, Fo), -121.8 (m, 2F, Fm), -155.3 [t, 1F, 3J(Fm-Fp)
max ∆F/e Å-3
compd
4
7
chem formula
cryst habit
cryst size/mm
cryst system
space group
a/Å
C30H15AuF10NP
yellow tapering prism yellow prism
0.22 × 0.15 × 0.12
triclinic
P1h
C68H48Au3Cl5F10NO4P3
0.32 × 0.16 × 0.09
triclinic
P1h
10.0862(8)
14.8036(12)
19.3597(16)
99.163(3)
98.068(3)
104.580(3)
2712.2(4)
4
13.4946(12)
14.2351(12)
18.5302(16)
77.029(3)
84.443(3)
83.508(3)
3437.1(5)
2
b/Å
c/Å
R/deg
â/deg
γ/deg
V/Å3
1
Z
) 19.9 Hz, Fp], -160.1(m, 2F, Fo). H NMR (CDCl3), δ: 7.58-7.08
Dc/g cm-3
M
1.977
1.927
1994.13
1904
(m, 14H, aromatic protons).
807.37
Crystal Structure Determinations. The crystals were mounted in
inert oil on glass fibers and transferred to the cold gas stream of a
Siemens P4 (2), Siemens SMART (3), or Bruker SMART (4, 7)
diffractometer. Data were collected using monochromated Mo KR
radiation (λ ) 0.710 73 Å) in ω-scan mode (2, 3) or with ω- and φ-scans
(4, 7). Absorption corrections were applied on the basis of ψ-scans for
2, whereas for 3, 4, and 7 the program SADABS, based on multiple
scans, was used. The structures were solved by Patterson (2, 4) or direct
methods (3, 7) and refined on F2 using the program SHELXL-97.37
All non-hydrogen atoms were refined anisotropically, except for solvent
carbon. Aminic hydrogens were located and refined using distance
restraints for 2 and 4. Other hydrogen atoms were included using a
riding model. Further crystal data are given in Table 1.
F(000)
T/°C
2θmax/deg
µ(Μo KR)/mm-1
transm
1544
-130
-130
60
60
5.575
6.726
0.945, 0.683
29 022
0.862, 0.555
59 536
19 933
0.0459
0.0227
0.0651
19 933
864
no. of reflcns measd
no. of unique reflcns 15 390
Rint
0.0466
0.0349
0.0617
15 390
783
737
0.802
1.514
Ra (F > 4σ(F))
wRb (F2, all reflcns)
no. of reflcns used
no. of params
no. of restraints
Sc
296
1.034
max ∆F/e Å-3
2.190
a R(F)) Σ||Fo | - |Fc||/Σ|Fo |. b wR (F2) ) [Σ{w(Fo - Fc2)2}/
2
Special Details of Refinement. 3: The structure contains two poorly
resolved molecules of dichloromethane, of which one is disordered over
an inversion center. The composition and derived parameters are based
on full occupation of these sites. 7: The structure contains three
dichloromethane sites, two of which are disordered over an inversion
center and are poorly defined. The composition and derived parameters
are based on two dichloromethane molecules per molecule of complex.
Most major features of residual electron density are in the solvent
region.
Σ{w(Fo )2}]0.5; w-1 ) σ2(Fo ) + (aP)2 + bP, where P ) [Fo2 + 2Fc2]/
2
2
3 and a and b are constants adjusted by the program. c S ) [Σ{w(Fo
2
- Fc2)2}/(n - p)]0.5, where n is the number of data and p the number
of parameters.
Results and Discussion
As mentioned above, only a few gold(I) complexes containing
the N,P-donor ligand PNH2 have been reported to date,12 and
no gold(III) complex at all; our first objective was thus the
synthesis of compounds of this type. Accordingly, treatment of
(37) Sheldrick, G. M. SHELXL-97, a program for crystal structure
refinement; University of Go¨ttingen: Go¨ttingen, Germany, 1997.

[Au(C6F5)2X(PNH2)] Complexes
Inorganic Chemistry, Vol. 40, No. 13, 2001 3021
Scheme 1a
a R ) C6F5. Key: (i) [AuR3(tht)]; (ii) 1/2 [AuR2(µ-Cl)]2; (iii) [AuR2(OEt2)2]ClO4; (iv) AgClO4; (v) [AuR2(acac)]; (vi) Tl(acac); (vii) PPN(acac);
(viii) [Ag(OClO3)(PPh3)]; (ix) [Au(OClO3)(PPh3)]; (x) [Au(acac)(PPh3)]; (xi) 2 [Au(acac)(PPh3)].
PNH2 with the gold(III) starting materials [Au(C6F5)3(tht)] or
[Au(C6F5)2(µ-Cl)]2 in the appropriate molar ratio, as illustrated
in Scheme 1, leads to the synthesis of the neutral gold(III)
complexes [Au(C6F5)3(PNH2)] (1) or [Au(C6F5)2Cl(PNH2)] (2),
in each of which the ligand is monodentate, coordinating the
gold center through the phosphorus atom.
Complexes 1 and 2 are air- and moisture-stable solids, soluble
in most common organic solvents and insoluble in hexane, with
elemental analyses and physical and spectroscopic properties
in accordance with the proposed stoichiometry. Their IR spectra
show the ν(N-H) stretching absorptions at 3380 and 3460 (1)
and 3370 and 3472 (2) cm-1 and also bands assignable to the
pentafluorophenyl groups bonded to gold(III).30,31
The 31P{1H} NMR spectra show a single resonance at 12.0
(1) or 20.7 (2) ppm that appears as a multiplet because of
coupling with fluorine. In the 19F NMR two groups of signals,
each corresponding to one type of pentafluorophenyl group, are
observed with relative intensities 2:1 (1) or 1:1 (2), confirming
Figure 1. Structure of compound 2 in the crystal showing the atom
numbering scheme. Radii are arbitrary. For clarity, only the aminic H
atoms are shown.
their cis disposition. The resonance of the aminic protons
1
appears in the H NMR at 3.8 (1) or 3.9 (2) ppm. Finally, the
found in 2 compare reasonably well with those found in [Cl-
(C6F5)2Au{Ph2PCH(AuNC5H5)PPh2}AuCl]38 (2.037(18), 2.052-
(20) Å) and [AuCl(CH3)2{Ph2PCH2PPh2O}]39 (2.042(5), 2.070-
(5) Å). The longer of the distances mentioned above are in the
range of values found in tris(pentafluorophenyl) gold deriva-
tives.40 The Au-Cl distance is (2.3230(11) Å), shorter than in
[Cl(C6F5)2Au{Ph2PCH(AuNC5H5)PPh2}AuCl]38 (2.337(8) Å),
[AuCl(CH3)2{Ph2PCH2PPh2O}]39 (2.391(1) Å), and [AuCl3-
(PPh3)]41 (2.347(4) Å for the chlorine trans to the triphenylphos-
phine; cf. 2.273(4) and 2.282(2) Å for the mutually trans chorine
atoms) but longer than the bond trans to N in [AuCl3(C6H7-
NO)]42 (2.265(3)-2.278(4) Å). It resembles the distances
peak from the molecular ion is observed in the mass spectrum
of 1 (FAB+) at m/z ) 975 (3%) with an experimental isotopic
distribution in accordance with calculation. Other peaks corre-
sponding to various fragments are also found: [Au(C6F5)2-
(PNH2)]+, [Au(C6F5)(PNH2)]+, and [Au(PNH2)]+ at m/z ) 808
(50), 641 (100), and 474 (70%) in 1 or [Au(C6F5)2(PNH2)]+
and [Au(PNH2)]+ at m/z ) 808 (65) and 474 (100%) in 2.
The crystal structure of 2 was determined by X-ray diffraction
studies on a crystal obtained by slow diffusion of hexane into
a solution of the complex in dichloromethane. The gold center
is coordinated by the ipso carbon atoms of two pentafluorophe-
nyl rings, one chlorine, and the phosphorus atom of the PNH2
ligand (Figure 1) and exhibits a square planar geometry with
angles from 86.09(14) to 93.32(10)° (a selection of bond lengths
and angles is shown in Table 2). The greater trans influence of
the PNH2 ligand, compared with chlorine, is reflected in the
Au-C distances. The bond trans to chlorine is 2.038(4) Å,
whereas that trans to PNH2 is 2.068(4) Å. There are few
examples in the literature of gold(III) centers coordinated by
two carbon atoms, a chlorine, and a P donor atom. The distances
(38) Uson, R.; Laguna, A.; Laguna, M.; Manzano, B. R.; Sheldrick, G.
M.; J. Chem. Soc., Dalton Trans. 1985, 2417
(39) Paul, M.; Schmidbaur, H. Chem. Ber. 1996, 129, 77
(40) See, for example: Bella, P. A.; Crespo, O.; Fernandez, E. J.; Fischer,
A. K.; Jones, P. G.; Laguna, A.; Lopez-de-Luzuriaga, J. M.; Monge,
M. J. Chem. Soc., Dalton Trans. 1999, 4009 and references therein.
(41) Bandori, G.; Clemente, D. A.; Marangoni, G.; Cattalina, L. J. Chem.
Soc., Dalton Trans. 1973, 866.
(42) Bruni, B.; Ferraroni, M.; Orioli, P.; Speroni, G. Acta Crystallogr. 1996,
C52, 1423

3022 Inorganic Chemistry, Vol. 40, No. 13, 2001
Table 2. Bond Lengths (Å) and Angles (deg) for 2
Ferna´ndez et al.
Au-C(21)
Au-C(11)
Au-Cl
2.038(4)
2.068(4)
2.3230(11)
2.3853(10)
1.812(4)
1.821(4)
1.819(4)
N-C(32)
1.383(5)
1.402(5)
1.411(5)
1.390(6)
1.378(6)
1.382(6)
1.370(5)
C(31)-C(36)
C(31)-C(32)
C(32)-C(33)
C(33)-C(34)
C(34)-C(35)
C(35)-C(36)
Au-P
P-C(31)
P-C(51)
P-C(41)
C(21)-Au-C(11)
C(21)-Au-Cl
C(11)-Au-Cl
C(21)-Au-P
C(11)-Au-P
Cl-Au-P
C(31)-P-C(51)
C(31)-P-C(41)
C(51)-P-C(41)
C(31)-P-Au
C(51)-P-Au
C(41)-P-Au
86.09(14) C(36)-C(31)-P
176.53(10) C(32)-C(31)-P
90.84(10) N-C(32)-C(33)
93.32(10) N-C(32)-C(31)
119.1(3)
121.6(3)
119.3(4)
122.1(4)
176.96(10) C(33)-C(32)-C(31) 118.6(4)
89.83(4) C(34)-C(33)-C(32) 121.0(4)
108.77(17) C(33)-C(34)-C(35) 120.5(4)
105.44(17) C(36)-C(35)-C(34) 119.7(4)
104.75(17) C(35)-C(36)-C(31) 121.0(4)
112.31(13) C(46)-C(41)-P
114.21(12) C(42)-C(41)-P
110.74(12) C(56)-C(51)-P
119.6(3)
120.4(3)
118.7(3)
121.5(3)
Figure 2. Structure of the cation of compound 3 in the crystal showing
the atom numbering scheme. Radii are arbitrary. For clarity, only the
aminic H atoms are shown.
C(16)-C(11)-Au 122.6(3)
C(12)-C(11)-Au 121.8(3)
C(52)-C(51)-P
solvents and insoluble in hexane. Its physical, analytical, and
spectroscopic properties agree with the proposed stoichiometry.
(2.324(2), 2.325(2) Å) trans to S found in [Ph3PNPPh3][Au-
(S2C2B10)Cl2].43 A longer Au-P distance (2.3853(10) Å) is
found in 2, compared with other phosphinogold(III) complexes,
such as [Me-C6H3{NHPPh2Au(C6F5)3}2] (2.346(2), 2.358(3)
Å),40 NBu4[{Au(C6F5)3(PPh2CHPPh2)}2Au]44 (2.367(2) Å), or
[AuMe3PPh3]45 (2.347(6) Å). It is similar to that observed in
[C6H4{NHPh2Au(C6F5)3}{N(AuPPh3)PPh2Au(C6F5)3}] (2.3829-
(15), 2.3615(16) Å).40
In the IR spectrum of 4, apart from the absorptions from the
perfluorophenyl groups, a sharp band at 3409 cm-1 is now
observed arising from the NH group. Compared with 3, the
resonance of the phosphorus atom appears in its 31P{1H} NMR
at higher field because of the deprotonation of the NH2 group.
1
This effect is also shown in the H NMR spectrum, where the
The C(31)-C(32) distance between the two carbons of the
PNH2 skeleton is 1.411(5) Å. The amine group forms an
intramolecular hydrogen bond to a fluorine atom: N-H02...-
F10, with H...F 2.30(4) Å and N-H...F 161(4)°.
In complexes 1 and 2 the ligand is monodentate, but it can
also behave as bidentate chelating ligand when treated with
equimolecular amounts of [Au(C6F5)2(OEt2)2]ClO4. This reac-
tion leads to the new cationic complex [Au(C6F5)2(PNH2)]ClO4
(3), which is soluble in chlorinated solvents and acetone and
insoluble in diethyl ether and hexane. It behaves as a uni-
univalent electrolyte in acetone solutions, and its elemental
analysis and spectroscopic properties agree with the proposed
stoichiometry.
signal of the NH is now located at 5.19 ppm. In its mass
spectrum (FAB+) the parent peak at m/z ) 807 corresponds to
M+.
To determine the structural differences between 3 and 4,
single crystals of both complexes were grown by diffusion of
hexane in a solution of the respective complex in dichlo-
romethane and their crystal structures were determined by X-ray
diffraction.
Compound 3 contains one independent formula unit in the
unit cell, whereas compound 4 contains two independent
molecules. In both complexes the gold atoms are bonded to
two pentafluorophenyl rings and chelated by the PNH2 (3) or
[PNH]- (4) ligands. The gold centers lie in the plane formed
by the four donor atoms and exhibit square planar geometries
(Figures 2 and 3). The narrowest angle is always that restricted
by the chelating ligand (see the selection of angles and bond
lengths in Tables 3 (compound 3) and 4 (compound 4)).The
distances Au-C are 2.019(6), 2.073(7) Å in 3 and 2.041(4),
2.067(4) Å for one of the molecules in 4 and 2.053(4), 2.050-
(5) Å in the other. The values in 3 clearly indicate a higher
trans effect of the PPh2 group than the NH2 group. In compound
4 the Au-C distances are more similar, indicating a higher trans
effect from the deprotonated NH group than from NH2. The
additional electron density delocalized through the Au-N-C
bonds is reflected in both the Au-N and N-C distances. The
Au-N distance in 3 is 2.107(5) Å, whereas those found in 4
are 2.028(4), 2.024(4) Å. Similarly, the N-C distance in 3 is
1.474(9) Å, whereas those found in 4 are shorter, 1.356(6),
1.359(6) Å. No noticeable differences are observed in the C-C
bond lengths between the carbon atoms bonded to the donor
atoms (P and N) in the PNH2 or [PNH]- ligands when
comparing both structures or compared with 2. The Au-P
distances (2.3222(18) Å in 3, 2.3254(13), 2.3174(13) Å in 4)
are shorter than those found for 2. In 3 the Au-N bond distances
compare well with those found in the derivatives [Au(C6F5)2-
The infrared spectrum of 3 displays a broad band at ∼3520
cm-1 from the NH2 group and bands from the perfluorophenyl
groups similar to those observed in 2, besides bands from the
anion at ∼1100 (vs, br) and 623 (m) cm-1 46
.
The 31P{1H} NMR
signal of the ligand is located at 45.1 ppm. The 19F NMR of 3
is similar to that registered for complex 2, and in its mass
spectrum (FAB+) the peak corresponding to the molecular
cation appears at m/z ) 808 (87%), while the largest peak
located at m/z ) 474 corresponds to the fragment [Au(PNH2)]+.
The neutral amido complex [Au(C6F5)2(PNH)] (4) can be
obtained by deprotonation of 3 with PPN(acac) or by treatment
of the chloro complex 2 with Tl(acac). Furthermore, reaction
of the free ligand with the (acetylacetonato)gold(III) derivative
[Au(C6F5)2(acac)] also leads to the synthesis of 4 through an
alternative pathway (see Scheme 1). This complex is obtained
as a stable yellow solid, soluble in most common organic
(43) Crespo. O.; Gimeno, M. C.; Jones, P. G.; Laguna, A. J. Organomet.
Chem. 1997, 547, 89.
(44) Fernandez, E. J.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Lo´pez-
de-Luzuriaga, J. M. Organometallics 1995, 14, 2918.
(45) Stein, J.; Fackler, J. P.; Paparizos, C.; Chen, H. W. J. Am. Chem.
Soc. 1981, 103, 2192.
(46) Hathaway, B. J.; Underhill, A. E. J. Chem. Soc. 1961, 3091.

[Au(C6F5)2X(PNH2)] Complexes
Inorganic Chemistry, Vol. 40, No. 13, 2001 3023
Figure 3. Structure of compound 4 in the crystal showing the atom numbering scheme. Radii are arbitrary. For clarity, only the aminic H atom
is shown.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 3
center through the nitrogen and two carbon atoms [Au(DPPY)-
(PPh3)], [Au2(DPPY)2(dppm)], and [Au(DPPY)(dppe)]50 (dppm
) bis(diphenylphosphino)methane, dppe ) 1,2-bis(diphenylphos-
phino)ethane) (distances between 2.019(16) and 2.040(1) Å).
As mentioned above, we were especially interested in the
synthesis of mixed gold(III)-M(I) compounds, to determine
whether metal-metal contacts can also appear in such com-
pounds. Thus, we treated the neutral derivative 4 with [Ag-
(OClO3)(PPh3)] or with a freshly prepared solution of [Au-
(PPh3)]ClO4 (1:1), isolating the new cationic complexes
[Au(C6F5)2{PNH(MPPh3)}]ClO4 (M ) Ag (5), Au (6)). Com-
plex 6 can also be obtained by direct reaction of 3 with an
equimolecular amount of [Au(acac)(PPh3)]. These species are
obtained as yellow (5) or orange (6) air- and moisture-stable
solids, soluble in chlorinated solvents and acetone and insoluble
in diethyl ether and hexane. They behave as uni-univalent
electrolytes, and their analytical and spectroscopic properties
agree with the proposed stoichiometry.
Their 31P{1H} NMR spectra display a new resonance from
the PPh3 bonded to the M(I) center. In the case of silver this
signal appears at room temperature as a doublet of multiplets
centered at 14.1 ppm that splits into a doublet of doublets
centered at 13.0 ppm when the temperature is decreased to 223
K. This pattern is due to the coupling of the phosphorus atom
of the triphenylphosphine ligand with both NMR-active isoto-
pomers of silver (109Ag and 107Ag) with coupling constants of
803 (109Ag-P) and 691 (107Ag-P) Hz. In the 31P{1H} NMR
of 6 the resonance of the PPh3 ligand is located at 29.3 ppm.
The phosphorus of the PPh2 group appears at 45.2 (5) or 42.4
(6) ppm.
Similarly to our observations in the 1H NMR spectrum of 3,
the resonance of the aminic proton seems to be masked by those
corresponding to the aromatic protons in these two complexes,
while the 19F NMR is similar to that registered for 3.
Finally, the peak due to the molecular cation is observed in
the mass spectra (ES+) at m/z ) 1177 (7, 5) or 1266 (95%, 6).
These spectra also display other peaks corresponding to the
fragments [AgPPh3]+ or [PNH(AuPPh3)]+ at m/z ) 670 (45,
5) or 736 (50%, 6), respectively.
Both protons of the PNH2 ligand can be replaced by AuPPh3
groups, and thus the trinuclear complex [Au(C6F5)2{PN-
(AuPPh3)2}]ClO4 (7) was obtained by reaction of 3 with [Au-
(acac)(PPh3)] (1:2) in dichloromethane or by treatment of 6 with
Au-C(51)
Au-C(41)
Au-N
2.019(6)
2.073(7)
2.107(5)
2.3222(18)
P-C(31)
P-C(12)
P-C(21)
N-C(11)
1.797(7)
1.798(7)
1.803(7)
1.474(9)
Au-P
C(51)-Au-C(41)
C(51)-Au-N
C(41)-Au-N
C(51)-Au-P
C(41)-Au-P
N-Au-P
88.6(2)
177.0(2)
93.5(2)
92.90(18)
172.17(19)
84.81(16)
C(31)-P-C(21)
C(12)-P-C(21)
C(31)-P-Au
C(12)-P-Au
C(21)-P-Au
C(11)-N-Au
110.3(3)
108.2(3)
106.9(2)
100.3(2)
121.2(2)
116.6(4)
Table 4. Selected Bond Lengths (Å) and Angles (deg) for 4
Au-N
2.028(4)
2.041(4)
2.067(4)
2.3254(13)
1.786(4)
1.792(4)
1.803(4)
1.356(6)
Au′-N′
2.024(4)
2.050(5)
2.053(4)
2.3174(13)
1.791(4)
1.803(5)
1.805(4)
1.359(6)
Au-C(41)
Au-C(31)
Au-P
Au′-C(31′)
Au′-C(41′)
Au′-P′
P-C(1)
P-C(11)
P-C(21)
N-C(2)
P′-C(1′)
P′-C(21′)
P′-C(11′)
N′-C(2′)
N-Au-C(41)
N-Au-C(31)
C(41)-Au-C(31)
N-Au-P
C(41)-Au-P
C(31)-Au-P
C(1)-P-C(11)
C(1)-P-C(21)
C(11)-P-C(21)
C(1)-P-Au
176.70(17) N′-Au′-C(31′)
94.10(16) N′-Au′-C(41′)
88.42(15) C(31′)-Au′-C(41′)
82.09(13) N′-Au′-P′
91.25(17)
178.91(17)
89.77(16)
82.98(13)
173.01(12)
96.04(12)
109.8(2)
105.96(19)
108.5(2)
99.54(16)
114.72(15)
117.42(15)
121.2(3)
95.44(12) C(31′)-Au′-P′
175.99(11) C(41′)-Au′-P′
110.2(2)
108.9(2)
C(1′)-P′-C(21′)
C(1′)-P′-C(11′)
106.96(19) C(21′)-P′-C(11′)
100.42(16) C(1′)-P′-Au′
116.92(15) C(21′)-P′-Au′
113.18(15) C(11′)-P′-Au′
C(11)-P-Au
C(21)-P-Au
C(2)-N-Au
122.0(3)
C(2′)-N′-Au′
(Fcpy)2]ClO4 (2.076(7), 2.089(7) Å) and [Au(C6F5)3(Fcpy)]47
(2.101(3) Å). A longer bond was found in [Au(TPB)Me2]48
(TPB ) 3,7-dimethyl-1,5,7-triaza-3-phosphabicyclo[3.3.1]-
nonane) (2.22(1) Å, in which the gold center is chelated by the
phosphabicyclo derivative). Shorter distances have been found
in other pyridine derivatives, such us [Au{dpk-(OH)2}-Cl2]Cl
(dpk ) di-2-pyridylmethanediol-N,N′)49 (2.039(5), 2.042(5) Å)
or in [AuCl3(C6H7NO)]42 (2.021(9) Å) and in compounds in
which 2,6-diphenylpyridine (DDPY) is coordinated to the gold
(47) Barranco, E. M.; Crespo, O.; Gimeno, M. C.; Jones, P. G.; Laguna,
A.; Villacampa, M. D. J. Organomet. Chem. 1999, 592, 258.
(48) Assmann, B.; Angermaier, K.; Paul, M.; Riede, J.; Schmidbaur, H.
Chem. Ber. 1985, 128, 891.
(49) Sommerer, S.; Jircitano, A. J.; Westcott, B. L.; Abboud, K. A.; Krause
Bauer, J. A. Acta Crystallogr. 1997, C53, 707.
(50) Wong, K.-H.; Cheung, K.-K.; Chan, M.C.-W.; Che, C.-M. Organo-
metallics 1988, 17, 3505.

3024 Inorganic Chemistry, Vol. 40, No. 13, 2001
Ferna´ndez et al.
Table 5. Selected Bond Lengths (Å) and Angles (deg) for 7
Au(1)-C(11)
Au(1)-N
Au(1)-C(1)
Au(1)-P(1)
Au(1)-Au(3)
Au(2)-N
2.046(3)
2.079(3)
2.088(4)
2.3113(9)
3.3219(3)
2.077(3)
Au(2)-P(2)
Au(2)-Au(3)
Au(3)-N
Au(3)-P(3)
P(1)-C(41)
N-C(46)
2.2395(9)
2.9749(3)
2.104(3)
2.2505(9)
1.790(3)
1.438(4)
C(11)-Au(1)-N
C(11)-Au(1)-C(1)
N-Au(1)-C(1)
176.81(12) P(3)-Au(3)-Au(1) 145.15(3)
87.07(13) Au(2)-Au(3)-Au(1) 67.190(8)
95.03(12) C(41)-P(1)-Au(1) 100.33(12)
93.39(9) C(21)-P(1)-Au(1) 115.46(11)
84.47(8) C(31)-P(1)-Au(1) 113.34(12)
179.12(10) C(61)-P(2)-Au(2) 111.91(11)
C(11)-Au(1)-P(1)
N-Au(1)-P(1)
C(1)-Au(1)-P(1)
C(11)-Au(1)-Au(3) 145.26(9) C(51)-P(2)-Au(2) 116.96(11)
N-Au(1)-Au(3)
C(1)-Au(1)-Au(3)
P(1)-Au(1)-Au(3)
N-Au(2)-P(2)
37.68(7) C(71)-P(2)-Au(2) 108.04(11)
82.50(9) C(91)-P(3)-Au(3) 115.42(13)
97.52(2) C(101)-P(3)-Au(3) 112.42(12)
174.17(7) C(81)-P(3)-Au(3) 109.89(12)
N-Au(2)-Au(3)
44.99(7) C(46)-N-Au(2)
116.5(2)
P(2)-Au(2)-Au(3) 129.33(2) C(46)-N-Au(1)
116.0(2)
Figure 4. Structure of the cation of compound 7 in the crystal showing
the atom numbering scheme. Radii are arbitrary. H atoms are omitted
for clarity.
N-Au(3)-P(3)
N-Au(3)-Au(2)
176.53(8) Au(2)-N-Au(1)
44.29(7) C(46)-N-Au(3)
114.51(12)
110.14(18)
90.72(10)
105.15(12)
P(3)-Au(3)-Au(2) 136.84(3) Au(2)-N-Au(3)
N-Au(3)-Au(1)
37.17(7) Au(1)-N-Au(3)
an equimolecular amount of the same acetylacetonate derivative.
This complex is obtained as a yellow solid with physical
properties similar to those observed for 6 and analytical data in
accordance with the proposed stoichiometry.
(2)-Au(3) 2.9749(3) Å) is present. The Au(I)-Au(III) distances
(Au(1)-Au(2) 3.4961(3) Å, Au(1)-Au(3) 3.3219(3) Å) are
noteworthy and may indicate the presence of weak interactions
between the gold(I) and gold(III) centers. We have previously
drawn attention to this possibility, as indicated by short gold-
(I)-gold(III) distances in some of our complexes and also by
theoretical studies.26,52 The difference in the Au-C bond lengths
is appreciable (2.046(3), 2.088(4) Å), with the longer bond trans
to the phosphorus atom. This situation resembles that found in
3. The Au(III)-N (2.079(3) Å) and Au(III)-P (2.3113(9) Å)
bond distances are similar to those found in 3.
The 31P{1H} NMR spectrum of 7 shows two resonances at
46.3 (PPh2) and 27.5 (AuPPh3) ppm, the latter with a higher
1
intensity, while in its H NMR spectrum only signals due to
aromatic protons are observed. The peak corresponding to the
molecular cation also appears in the mass spectrum (ES+) of 7
at m/z ) 1725 (16%).
Finally, X-ray diffraction studies were carried out on a single
crystal of 7 grown by slow diffusion of n-heptane in a solution
of 7 in dichloromethane. The molecule involves a [PN]2- ligand
that chelates a gold(III) center, also bonded to two pentafluo-
rophenyl rings. The nitrogen atom is also bonded to two AuPPh3
fragments (Figure 4) resembling the structure found in the
trinuclear complex of 8-aminoquinoline.51 The gold(III) center
exhibits the usual square planar geometry. As seen in complexes
2-4, the narrowest angle is, once again, that restricted by the
bite angle of the ligand (N-Au(1)-P(1) 84.47(8)°) (see Table
5). Linear geometry at both gold(I) centers is observed, with
N-Au(2)-P(2) 174.17(7)° and N-Au(3)-P(3) 176.53(8)°. An
intramolecular interaction between the two gold(I) centers (Au-
Acknowledgment. We thank the Direccio´n General de
Ensen˜anza Superior (Grant No. PB97-1010-C02-02), the Fonds
der Chemischen Industrie, and the CAI (Caja de Ahorros de la
Inmaculada) for financial support.
Supporting Information Available: CIF files of crystal data, data
collection and solution and refinement parameters, bond distances and
angles, and anisotropic thermal parameters. This material is available
free of charge via the Internet at http://pubs.acs.org.
IC0100875
(52) (a) Crespo, O.; Canales, F.; Gimeno, M. C.; Jones, P. G.; Laguna, A.
Organometallics 1999, 18, 3142. (b) Canales, F.; Gimeno, M. C.;
Laguna, A.; Jones, P. G. Organometallics 1996, 15, 3412.
(51) Schmidbaur, H.; Kolb, A.; Bissinger, P. Inorg. Chem. 1992, 31, 4370.