Gold(I) Complexes with N-Donor Ligands. 2.1 Reactions of Ammonium Salts with [Au(acac-κC2)(PR3)] to Give [Au(NH3)L]+,[(AuL)2(μ2-NH 2)]+,[(AuL)4(μ4-N)]+, or [(AuL)3(μ3-O)]+. A New and Facile Synthesis of

Article abstract of DOI:10.1021/ic970225j

The complexes [Au(acac-κC²)(PR₃)] (acac = acetylacetonate, R = Ph, C₆H₄OMe-4) react with (NH₄)ClO₄ to give amminegold(I), [Au(NH₃)(PR₃)]ClO₄, amidogold(I), [(AuPR₃)₂(μ₂-NH₂)]ClO ₄, or nitridogold(I), [(AuPR₃)₄(μ₄-N)]ClO₄, complexes, depending on the reaction conditions. Similarly, [Au(acac-κC²)(PPh₃)] reacts with (NH₃R')OTf (OTf = CF₃SO₃) (1:1) or with [H₃N(CH₂)₂NH₂]OTf (1:1) to give (amine)gold(I) complexes [Au(NH₂R')(PPh₃)]OTf (R' = Me, C₆H₄NO₂-4) or [(AuPPh₃)₂{μ₂-H₂N(CH ₂)₂NH₂}](OTf)₂, respectively. The ammonium salts (NH₂R'₂)OTf (R' = Et, Ph) react with [Au(acac-κC²)(PR₃)] (R = Ph, C₆H₄OMe-4) (1:2) to give, after hydrolysis, the oxonium salts [(AuPR₃)₃(μ₃-O)]OTf (R = Ph, C₆H₄OMe-4). When NH₃ is bubbled through a solution of [AuCl(tht)] (tht = tetrahydrothiophene), the complex [Au(NH₃)₂]Cl precipitates. Addition of [Au(NH₃)₂]Cl to a solution of AgClO₄ or TlOTf leads to the isolation of [Au(NH₃)₂]ClO₄ or [Au(NH₃)₂]OTf, respectively. The crystal structure of [(AuPR₃)₃(μ₃-O)]OTf-Me₂CO (R = C₆H₄OMe-4) has been determined: triclinic, space group P1?, a = 14.884(3) A?, b = 15.828(3) A?, c = 16.061(3) A?, α = 83.39(3)°, β = 86,28(3)°, γ - 65.54(3)°, R1 (wR2) = 0.0370 (0.0788). The [(AuPR₃)₃(μ₃-O)]⁺ cation shows an essentially trigonal pyramidal array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175° and Au?Au contacts in the range 2.9585(7)-3.0505(14) A?. These cations are linked into centrosymmetric dimers through two short Au?Au [2.9585(7), 3.0919(9) A?] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.

Full text of DOI:10.1021/ic970225j

4438
Inorg. Chem. 1997, 36, 4438-4443
Gold(I) Complexes with N-Donor Ligands. 2.1 Reactions of Ammonium Salts with
[Au(acac-KC2)(PR3)] To Give [Au(NH3)L]+, [(AuL)2(µ2-NH2)]+, [(AuL)4(µ4-N)]+, or
[(AuL)3(µ3-O)]+. A New and Facile Synthesis of [Au(NH3)2]+ Salts. Crystal Structure of
[{AuP(C6H4OMe-4)3}3(µ3-O)]CF3SO3
Jose´ Vicente,*,† Mar´ıa-Teresa Chicote,* and Rita Guerrero
Grupo de Qu´ımica Organometa´lica,‡ Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica,
Universidad de Murcia, Apartado 4021, Murcia, 30071 Spain
Peter G. Jones*,§ and M. Carmen Ram´ırez de Arellano|
Institut fu¨r Anorganische und Analytische Chemie, Technische Universita¨t Braunschweig, Postfach 3329,
38023 Braunschweig, Germany
ReceiVed February 26, 1997X
The complexes [Au(acac-κC2)(PR3)] (acac ) acetylacetonate, R ) Ph, C6H4OMe-4) react with (NH4)ClO4 to
give amminegold(I), [Au(NH3)(PR3)]ClO4, amidogold(I), [(AuPR3)2(µ2-NH2)]ClO4, or nitridogold(I), [(AuPR3)4-
(µ4-N)]ClO4, complexes, depending on the reaction conditions. Similarly, [Au(acac-κC2)(PPh3)] reacts with
(NH3R′)OTf (OTf ) CF3SO3) (1:1) or with [H3N(CH2)2NH2]OTf (1:1) to give (amine)gold(I) complexes [Au-
(NH2R′)(PPh3)]OTf (R′ ) Me, C6H4NO2-4) or [(AuPPh3)2{µ2-H2N(CH2)2NH2}](OTf)2, respectively. The
ammonium salts (NH2R′2)OTf (R′ ) Et, Ph) react with [Au(acac-κC2)(PR3)] (R ) Ph, C6H4OMe-4) (1:2) to give,
after hydrolysis, the oxonium salts [(AuPR3)3(µ3-O)]OTf (R ) Ph, C6H4OMe-4). When NH3 is bubbled through
a solution of [AuCl(tht)] (tht ) tetrahydrothiophene), the complex [Au(NH3)2]Cl precipitates. Addition of [Au-
(NH3)2]Cl to a solution of AgClO4 or TlOTf leads to the isolation of [Au(NH3)2]ClO4 or [Au(NH3)2]OTf,
respectively. The crystal structure of [(AuPR3)3(µ3-O)]OTf‚Me2CO (R ) C6H4OMe-4) has been determined:
triclinic, space group P1h, a ) 14.884(3) Å, b ) 15.828(3) Å, c ) 16.061(3) Å, R ) 83.39(3)°, â ) 86.28(3)°,
γ ) 65.54(3)°, R1 (wR2) ) 0.0370 (0.0788). The [(AuPR3)3(µ3-O)]+ cation shows an essentially trigonal pyramidal
array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175° and Au‚‚‚Au contacts in
the range 2.9585(7)-3.0505(14) Å. These cations are linked into centrosymmetric dimers through two short
Au‚‚‚Au [2.9585(7), 3.0919(9) Å] contacts. The gold atoms of the dimer form a six-membered ring with a chair
conformation.
Introduction
NH2)]+, and [(AuPR3)3(µ3-NH)]+, are still unknown. Schmid-
baur has studied the reaction between [(AuPR3)3(µ3-O)]+ (R )
tBu) and a large excess of ammonia and obtained mixtures for
which FAB mass spectra show, as parent peaks, those corre-
sponding to [(AuPR3)2(µ2-NH2)]+ or [(AuPR3)3(µ3-NH)]+ com-
plexes depending on the Au:NH3 molar ratio.12 In this paper,
we report the first isolation of complexes of the types [Au-
(NH3)(PR3)]+ and [(AuPR3)2(µ2-NH2)]+, as well as [(AuPR3)4-
(µ4-N)]+, from (NH4)ClO4 and [Au(acac-κC2)(PR3)]. A fully
aurated complex derived from [H3N-NH3]2+ has been iso-
lated.13
Although the affinity of gold for nitrogen is low and most
compounds with gold-nitrogen bonds are of limited stability,2
+
examples of all possible aurated ammonium salts [(AuL)nNR4-n
]
(n ) 1-4)3-10 and even hypercoordinated complexes [(AuL)5-
(µ5-N)]2+ 4,11 have been reported. However, the first three
members of these series, i.e., [Au(NH3)(PR3)]+, [(AuPR3)2(µ2-
† E-mail: jvs@fcu.um.es.
‡ WWW: http://www.scc.um.es/gi/gqo/.
§ E-mail: jones@xray36.anchem.nat.tu-bs.de.
| Present address: Grupo de Qu´ımica Organometa´lica, Departamento de
Qu´ımica Inorga´nica, Facultad de Qu´ımica, Universidad de Murcia, Apartado
4021, Murcia, 30071 Spain.
We have previously shown that (acetylacetonato)gold(I)
complexes are useful reagents for preparing neutral, cationic,
and anionic gold(I) complexes with alkyl,14 alkynyl (including
ethynyl),14,15 hydrosulfido,16 phosphido,17 thiolato,18 ylide,14,15,19
X Abstract published in AdVance ACS Abstracts, August 15, 1997.
(1) Vicente, J.; Chicote, M. T.; Guerrero, R.; Jones, P. G. J. Chem. Soc.,
Dalton Trans. 1995, 1251.
(2) Puddephatt, R. J. In ComprehensiVe Coordination Chemistry; Wilkin-
son, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon: Oxford,
U.K., 1987; Vol. 5.
(3) Slovokhotov, Y. L.; Struchkov, Y. T. J. Organomet. Chem. 1984, 277,
143. Ramamoorthy, V.; Sharp, P. R. Inorg. Chem. 1990, 29, 336.
Schmidbaur, H.; Kolb, A.; Bissinger, P. Inorg. Chem. 1992, 31, 4370.
(4) Angermaier, K.; Schmidbaur, H. Chem. Ber. 1995, 128, 817.
(5) Perevalova, E. G.; Grandberg, K. I.; Smyslova, E. I.; Kuz’mina, L.
G.; Korsunskii, V. I.; Kravtsov, D. N. Organomet. Chem. USSR 1989,
2, 523.
(6) Angermaier, K.; Schmidbaur, H. J. Chem. Soc., Dalton Trans. 1995,
559.
(7) Kolb, A.; Bissinger, P.; Schmidbaur, H. Z. Anorg. Allg. Chem. 1993,
619, 1580.
(8) Perevalova, E. G.; Smyslova, E. I.; Djadchenko, V. P.; Grandberg,
K. I.; Nesmeyanov, A. N. IzV. Akad Nauk SSSR, Ser. Khim. 1980,
1455; Chem. Abstr. 1980, 93, 178615h.
(9) Lange, P.; Beruda, H.; Hiller, W.; Schmidbaur, H. Z. Naturforsch., B
1994, 49, 781.
(10) Grohmann, A.; Riede, J.; Schmidbaur, H. Z. Naturforsch., B 1992,
47, 1255.
(11) Angermaier, K.; Schmidbaur, H. Inorg. Chem. 1995, 34, 3120.
Grohmann, A.; Riede, J.; Schmidbaur, H. Nature 1990, 345, 140.
(12) Sladek, A.; Schmidbaur, H. Z. Naturforsch., B 1995, 50, 859.
(13) Ramamoorthy, V.; Wu, Z. D.; Yi, Y.; Sharp, P. R. J. Am. Chem. Soc.
1992, 114, 1526. Shan, H.; Yan, Y.; James, A. J.; Sharp, P. R. Science
1997, 275, 1460.
S0020-1669(97)00225-5 CCC: $14.00 © 1997 American Chemical Society

Gold(I) Complexes with N-Donor Ligands
Inorganic Chemistry, Vol. 36, No. 20, 1997 4439
and amine, [Au(NR3)L]+ (NR3 ) primary, secondary, or tertiary
amines), ligands.1 We also report here some attempts to use
this method to prepare complexes of the type [(AuL)2(µ2-
NR2)]+, whose number is very limited.4-7
Recently, Mingos presented a preliminary report on the
synthesis of [Au(NH3)2]X (X ) BF4, SbF6, Br).20 The full paper
corresponding to this work appeared while this paper was being
reviewed.21 We describe a different preparation of other salts
of this interesting gold(I) complex in almost quantitative yield,
and we recently used this complex to prepare (acetimine)-
gold(I) complexes.22
2 mL. Addition of diethyl ether (20 mL), filtration, washing the solid
with diethyl ether, recrystallization from THF and diethyl ether, and
finally washing the solid with pentane gave 1a. Yield: 262 mg,
76%. Mp: 95 °C. ΛM ) 132 Ω-1‚cm2‚mol-1 (3 × 10-4 mol‚L-1).
IR: ν(NH) 3173, 3244, 3318 cm-1 1H NMR (300 MHz, CDCl3; δ):
.
3.85 (s, br, 3H, NH3), 7.44-7.57 (m, 15H, Ph). 31P{1H} NMR (300
MHz, CDCl3; δ): 30.79 (s). Anal. Calcd for C18H18AuClNO4P: C,
37.55; H, 3.15; N, 2.43. Found: C, 37.50; H, 3.11; N, 2.24.
[Au(NH3){P(C6H4OMe-4)3}]ClO4 (1b). This complex was simi-
larly prepared from [Au(acac-κC2){P(C6H4OMe-4)3}] (359 mg,
0.55 mmol) and (NH4)ClO4 (72 mg, 0.61 mmol). Yield: 276 mg,
75%. Mp: 166 °C. ΛM ) 91 Ω-1‚cm2‚mol-1 (4 × 10-4 mol‚L-1).
IR: ν(NH) 3172, 3249, 3329 cm-1 1H NMR (300 MHz, CDCl3; δ):
.
3.76 (s, br, 3H, NH3), 3.84 (s, 9H, Me), 6.99 (dd, 6H, C6H4, 3JHH ) 9
Hz, 4JPH ) 1.8 Hz), 7.45 (dd, 6H, C6H4, 3JPH ) 6.9 Hz). 31P{1H} NMR
(121 MHz, CDCl3; δ): 26.7 (s). Anal. Calcd for C21H24AuClNO7P:
C, 37.88; H, 3.63; N, 2.10. Found: C, 38.28; H, 3.61; N, 2.01.
[(AuPPh3)2(µ2-NH2)]ClO4 (2a). [Au(acac-κC2)(PPh3)] (174 mg,
0.31 mmol) and [Au(NH3)(PPh3)]ClO4 (1a) (150 mg, 0.26 mmol) were
mixed together in a twin-necked flask. The flask was evacuated and
filled with N2 several times, and degassed CH2Cl2 (5 mL) was then
added. The resulting mixture was stirred for 10 min under N2 and
concentrated to 1 mL, and diethyl ether (20 mL) was added to give an
off-white solid that was recrystallized from CH2Cl2 and diethyl ether.
Yield: 211 mg, 78%. Mp: 111 °C. ΛM ) 110 Ω-1‚cm2‚mol-1 (3 ×
Experimental Section
IR and NMR spectroscopy, elemental analyses, conductance mea-
surements in acetone, and melting point determinations were carried
out as described elsewere.23 Chemical shifts are referred to TMS (1H)
or H3PO4 [31P{1H}]. Mass spectra (FAB+) were measured with a Fisons
VG-Autospec spectrometer using 3-nitrobenzyl alcohol as the matrix.
Unless otherwise stated, all reactions were carried out at room
temperature and without special precautions against moisture. The
solvents were distilled over Na/benzophenone (THF, diethyl ether), P2O5
and then Na2CO3 (dichloromethane), CaCl2 (n-hexane), and KMnO4
(acetone). n-Pentane was used as received. Warning! perchlorate
salts with organic cations may be explosive.
10-4 mol‚L-1). IR: ν(NH) 3248, 3323 cm-1 1H NMR (300 MHz,
.
[Au(acac-κC2)(PPh3)] was prepared as previously described.24 The
same method was successfully applied to the synthesis of [Au(acac-
κC2){P(C6H4OMe-4)3}]. Yield: 78%. Anal. Calcd for C26H28-
AuO5P: C, 48.16; H, 4.35. Found: C, 47.84; H, 3.47. NMR, δ: 1H
(CDCl3, 300 MHz) 2.37 (s, 6H, Me), 3.84 (s, 9H, OMe), 4.59 (d, 1H,
CDCl3; δ): 2.58 (s, br, 2H, NH2), 7.38-7.55 (m, 30H, Ph). 31P{1H}
NMR (121 MHz, CDCl3; δ): 30.72 (s). Mass spectrum: m/z
+
(assignment, percent abundance) 459 (AuPR3+, 35), 721.5 [Au(PR3)2
,
22], 934.2 (M+, 100). Anal. Calcd for C36H32Au2ClNO4P2: C, 41.82;
H, 3.12; N, 1.36. Found: C, 41.73; H, 3.02; N, 1.34.
3
CH, JHP 10 Hz), 6.95 (m, 6H, C6H4), 7.34 (m, 6H, C6H4); 31P{1H}
[{Au{P(C6H4OMe-4)3}}2(µ2-NH2)]ClO4 (2b). [Au(acac-κC2)-
{P(C6H4OMe-4)3}] (117 mgr, 0.18 mmol) was dissolved in degassed
CH2Cl2 (5 mL), the solution was filtered, and the filtrate was added
dropwise to a solution of [Au(NH3){P(C6H4OMe-4)3}]ClO4 (1b) (120
mg, 0.18 mmol) in CH2Cl2 (10 mL). The resulting mixture was fil-
tered through Celite, the filtrate was concentrated to 2 mL, and
diethyl ether (20 mL) was added to precipitate a cream-colored
solid, which was washed with diethyl ether (3 × 15 mL) to give 2b.
Yield: 167 mg, 76%. Mp: 99 °C. ΛM ) 123 Ω-1‚cm2‚mol-1 (5 ×
(121 MHz) 35.04 (s). [Ph2NH2]OTf and [Et2NH2]OTf were prepared
according to literature methods.1 Similarly, dropwise addition of
HO3SCF3 to a solution of ethylenediamine (1:1 molar ratio) in diethyl
ether precipitated [NH3(CH2)2NH2]OTf as a white solid. Yield: 99%.
Mp: 82 °C. Anal. Calcd for C3H9F3N2O3S: C, 17.14; H, 4.32; N,
13.33; S, 15.26. Found: C, 17.21; H, 4.34; N, 13.14; S, 16.26. 1H
NMR, δ (acetone-d6, 200 MHz): 2.87-4.06 (complex set of multiplets).
(NH4)ClO4 was purchased from Probus and recrystallized from acetone
and diethyl ether.
[Au(NH3)(PPh3)]ClO4 (1a). [Au(acac-κC2)(PPh3)] (337 mg, 0.60
mmol) was dissolved in 10 mL of tetrahydrofuran (THF), and the
solution was added dropwise to a suspension of (NH4)ClO4 (78 mg,
0.66 mmol) in THF (10 mL). The resulting mixture was stirred for 1
h and then filtered through Celite, and the filtrate was concentrated to
10-4 mol‚L-1). IR: ν(NH) 3268, 3332 cm-1 1H NMR (300 MHz,
.
CDCl3; δ): 2.37 (br, 2H, NH2), 3.82 (s, 18 H, Me), 6.83 (dd, 12H,
3
4
3
C6H4, JHH ) 8.7 Hz, JPH ) 1.8 Hz), 7.313 (dd, 12H, C6H4, JPH
)
12.7 Hz). 31P{1H} NMR (121 MHz, CDCl3; δ): 26.6 (s). Mass
spectrum: m/z (assignment, percent abundance) 2210 ([(AuPR3)4-
(µ4-N)], 8), 1114 (M+, 86), 901 [Au(PR3)2+, 33], 549 (AuPR3+, 100).
Anal. Calcd for C42H44Au2ClNO10P2: C, 41.55; H, 3.65; N, 1.15.
Found: C, 41.46; H, 3.55; N, 1.08
(14) Vicente, J.; Chicote, M. T.; Saura-Llamas, I.; Lagunas, M. C. J. Chem.
Soc., Chem. Commun. 1992, 915.
[(AuPPh3)4(µ4-N)]ClO4 (3a). Solid (NH4)ClO4 (7.36 mg, 0.063
mmol) was added to a solution of [Au(acac-κC2)(PPh3)] (140 mg, 0.25
mmol) in THF (15 mL). The initial solution was stirred, forming a
suspension, which was then stirred for 1.5 h. Volatiles were removed
in Vacuo, and the oily residue was washed with diethyl ether (2 × 10
mL) and then stirred in diethyl ether (15 mL) for 3 h. 3a appeared as
a pale cream-colored solid, which was filtered off, washed with diethyl
ether (5 mL), and dried under nitrogen. Yield: 86 mg, 70%. Mp:
203 °C dec. ΛM ) 108 Ω-1‚cm2‚mol-1 (10-4 mol‚L-1). 1H NMR
(300 MHz, CDCl3; δ): 7.09-7.47 (m, Ph). 31P{1H} NMR (121 MHz,
-60 °C, CDCl3; δ): 28.302 (no well-defined triplet). Anal. Calcd
for C72H60Au4ClNO4P4: C, 44.34; H, 3.10; N, 0.72. Found: C, 44.20;
H, 3.03; N, 0.55.
[{AuP(C6H4OMe-4)3}4(µ4-N)]ClO4 (3b). Solid (NH4)ClO4 (6.8
mg, 0.057 mmol) was added to a solution of [Au(acac-κC2)-
{P(C6H4OMe-4)3}] (150 mg, 0.23 mmol) in THF (15 mL), and the
resulting suspension was stirred for 2.5 h and then filtered. The pale
yellow filtrate was concentrated (1 mL), and diethyl ether (20 mL)
was added to precipitate an oily solid, which was washed with diethyl
ether (2 × 10 mL) and recrystallized from dichloromethane and diethyl
ether to give 3b as a pale cream-colored solid, which was filtered off
and dried under nitrogen atmosphere. Yield: 80 mg, 60%. Mp: 104
°C. ΛM ) 126 Ω-1‚cm2‚mol-1 (2 × 10-4 mol‚L-1). 1H NMR (300
MHz, CDCl3; δ): 3.80 (s, 3 H, OMe), 6.71 (dd, 2H, C6H4, 3JHH ) 8.4
(15) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D. J. Chem. Soc., Dalton
Trans. 1995, 497.
(16) Vicente, J.; Chicote, M. T.; Gonza´lez-Herrero, P.; Jones, P. G.; Ahrens,
B. Angew. Chem., Int. Ed. Engl. 1994, 33, 1852.
(17) Vicente, J.; Chicote, M. T.; Jones, P. G. Inorg. Chem. 1993, 32, 4960.
(18) Vicente, J.; Chicote, M. T.; Gonza´lez-Herrero, P.; Jones, P. G. J. Chem.
Soc., Dalton Trans. 1994, 3183.
(19) Vicente, J.; Chicote, M. T.; Cayuelas, J. A.; Fernandez-Baeza, J.; Jones,
P. G.; Sheldrick, G. M.; Espinet, P. J. Chem. Soc., Dalton Trans. 1985,
1163. Vicente, J.; Chicote, M. T.; Saura-Llamas, I.; Turpin, J.;
Fernandez-Baeza, J. J. Organomet. Chem. 1987, 333, 129. Vicente,
J.; Chicote, M. T.; Saura-Llamas, I.; Jones, P. G.; Meyer-Ba¨se, K.;
Erdbru¨gger, C. F. Organometallics 1988, 7, 997. Vicente, J.; Chicote,
M. T.; Saura-Llamas, I. J. Chem. Soc., Dalton Trans. 1990, 1941.
Vicente, J.; Chicote, M. T.; Lagunas, M. C.; Jones, P. G. J. Chem.
Soc., Dalton Trans. 1991, 2579. Vicente, J.; Chicote, M. T.; Lagunas,
M. C.; Jones, P. G. J. Chem. Soc., Chem. Commun. 1991, 1730.
Vicente, J.; Chicote, M. T.; Lagunas, M. C. Inorg. Chem. 1993, 32,
3748. Vicente, J.; Chicote, M. T.; Guerrero, R.; Jones, P. G. J. Am.
Chem. Soc. 1996, 118, 699.
(20) Mingos, D. M. P.; Yau, J.; Menzer, S.; Williams, D. J. J. Chem. Soc.,
Dalton Trans. 1995, 319.
(21) Yau, J.; Mingos, D. M. P. J. Chem. Soc., Dalton Trans. 1997, 1103.
(22) Vicente, J.; Chicote, M. T.; Abrisqueta, M. D.; Guerrero, R.; Jones,
P. G. Angew. Chem., Int. Ed. Engl. 1997, 36, 1203.
(23) Vicente, J.; Abad, J. A.; Ferna´ndez-de-Bobadilla, R.; Jones, P. G.;
Ram´ırez de Arellano, M. C. Organometallics 1996, 15, 24.
(24) Gibson, D.; Johnson, B. F. G.; Lewis, J. J. Chem. Soc. A 1970, 367.

4440 Inorganic Chemistry, Vol. 36, No. 20, 1997
Vicente et al.
4
3
Hz, JPH ) 1.2 Hz), 7.31 (dd, 2H, C6H4, JPH ) 12.6 Hz). 31P{1H}
NMR (121 MHz, CDCl3; δ): 20.21 (s). 13C NMR (75 MHz, CDCl3;
δ): 55.62 (s, OMe), 115.08 (d, C6H4, 3JCP ) 13 Hz), 119.79 (d, C6H4,
Table 1. Crystal Data for 7b‚Me2CO
empirical formula
Mr
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V(Å3)
Z
T (K)
C67H69Au3F3O14P3S
1871.09
P1h
1JCP ) 67.5 Hz), 135.22 (d, C6H4, JCP ) 15.1 Hz), 162.47 (s). Mass
2
spectrum (FAB): m/z (assignment, percent abundance) 2211.1 (M+,
100), 1662.4 [HN(AuPR3)3+, 6.3], 1114.2 [H2N(AuPR3)2+, 31.1],
901 [Au(PR3)2+, 39.6], 549.1 [AuPR3+, 65.2]. Anal. Calcd for
C84H84Au4ClNO16P4: C, 43.66; H, 3.66; N, 0.61. Found: C, 43.57;
H, 3.56; N, 0.54.
14.884(3)
15.828(3)
16.061(3)
83.39(3)
86.28(3)
65.54(3)
3421(1)
2
173(2)
Mo KR (0.710 73)
1.817
1816
6.588
12 058
484
425
0.0370
0.0869
1.04
[Au(NH2Me)(PPh3)]OTf (4). [Au(acac-κC2)(PPh3)] (250 mg, 0.45
mmol) was added to a suspension of (NH3Me)OTf (81 mg, 0.45 mmol)
in diethyl ether (15 mL). The resulting suspension was stirred for 3 h
and filtered, and the cream-colored solid was washed with diethyl ether
(3 × 20 mL) and recrystallized from CH2Cl2 and diethyl ether to give
4. Yield: 218 mg, 76%. Mp: 146 °C dec. ΛM ) 120 Ω-1‚cm2‚mol-1
λ (Å)
F
calc (g cm-3
)
F(000)
(4.5 × 10-4 mol‚L-1) IR: ν(NH) 3148, 3234 cm-1
.
1H NMR (300
µ, mm-1
MHz, CDCl3; δ): 2.81 (t, 3H, Me, 3JHH ) 5.8 Hz), 4.58 (br, 2H, NH2),
7.47-7.59 (m, 15H, Ph). 31P{1H} NMR (121 MHz, CDCl3; δ): 30.52
(s). Anal. Calcd for C20H20AuF3NO3PS: C, 37.57; H, 3.18; N, 2.19;
S, 5.02. Found: C, 37.80; H, 3.19; N, 2.19; S, 4.96.
no. of independent reflections
no. of parameters
no. of restraints
R1a
wR2b
[Au(NH2C6H4NO2-4)(PPh3)]OTf (5). [Au(acac-κC2)(PPh3)] (196
mg, 0.35 mmol) was added to a suspension of (NH3C6H4NO2-4)OTf
(101 mg, 0.35 mmol) in diethyl ether (15 mL). The resulting suspension
was stirred for 5 h and filtered, and the cream-colored solid was washed
with diethyl ether (3 × 20 mL) and recrystallized from dichloromethane
and diethyl ether to give 5. Yield: 184 mg, 70%. Mp: 153 °C. ΛM
) 108 Ω-1‚cm2‚mol-1 (4 × 10-4 mol‚L-1). IR: ν(NH) 3066, 3175
S(F2)
max ∆F (e Å-3
)
1.3
a R1 ) ∑||Fo| - |Fc||/∑|Fo| for reflections with I > 2σ(I). b wR2 )
2
2
[∑[w(Fo - Fc2)2]/∑[w(Fo )2]]0.5 for all reflections; w-1 ) σ2(F2) +
(aP)2 + bP, where P ) (2Fc2 + Fo )/3 and a and b are constants set by
the program.
2
cm-1 1H NMR (300 MHz, CDCl3; δ): 7.39-7.56, 7.99, 8.02 (m, 19
.
H, Ph + C6H4). 31P{1H} NMR (121 MHz, CDCl3; δ): 29.92 (s). Anal.
Calcd for C25H21AuF3N2O5PS: C, 40.07; H, 2.83; N, 3.74; S, 4.28.
Found: C, 40.35; H, 2.83; N, 3.79; S, 4.33.
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
7b‚Me2CO
Au(1)-Au(2)
Au(2)-Au(3)
Au(1)-O(1)
Au(3)-O(1)
Au(2)-P(2)
3.0505(14)
3.0078(7)
2.063(4)
2.066(4)
2.210(2)
Au(1)-Au(3)
Au(1)-Au(3)a
Au(2)-O(1)
Au(1)-P(1)
Au(3)-P(3)
2.9585(7)
3.0919(9)
2.026(5)
2.222(2)
2.219(2)
[(AuPPh3)2{µ2-H2N(CH2)2NH2}](OTf)2 (6). To a suspension of
(H2NCH2CH2NH3)OTf (75 mg, 0.36 mmol) in diethyl ether (20
mL) was added [Au(acac-κC2)(PPh3)] (200 mg, 0.36 mmol). The
resulting suspension was stirred for 15 h and filtered, and the resulting
solid was washed with diethyl ether (3 × 15 mL) and recrystallized
from CH2Cl2 and diethyl ether to give 6 as a cream-colored solid.
Yield: 163 mg, 68%. Mp: 166 °C dec. ΛM ) 169 Ω-1‚cm2‚mol-1
(6 × 10-4 mol‚L-1). IR: ν(NH) 3193, 3110, δ(NH2): 1589 cm-1. 1H
NMR (300 MHz, CDCl3; δ): 3.48 (s, 4H, CH2), 7.48-7.56 (m, 30H,
Ph). 31P{1H} NMR (121 MHz, CDCl3; δ): 30.3 (s). Anal. Calcd for
C40H38Au2F6N2O6P2S2: C, 37.63; H, 3.00; N, 2.19; S, 5.02. Found:
C, 37.59; H, 3.11; N, 2.26; S, 5,23.
[(AuPPh3)3(µ3-O)]OTf (7a). A solution of (Et2NH2)OTf (38 mg,
0.17 mmol) in acetone (10 mL) was added dropwise to a solution of
[Au(acac-κC2)(PPh3)] (220 mg, 0.39 mmol) in acetone (10 mL). After
the reaction mixture was stirred for 10 h, the formation of some metallic
gold was observed. The suspension was filtered through anhydrous
MgSO4, and the clear solution obtained was concentrated (2 mL). Upon
addition of diethyl ether (20 mL), complex 7a precipitated as a white
solid, which was filtered off, washed with diethyl ether (2 × 5 mL),
and air-dried. Yield: 62 mg, 31%. Mp: 222 °C dec. ΛM ) 103
Ω-1‚cm2‚mol-1 (1.13 × 10-4 mol‚L-1). 1H NMR (300 MHz, CDCl3;
δ): 7.3-7.6 (m, Ph). 31P{1H} NMR (121 MHz, CDCl3; δ): 23.69
(s). Anal. Calcd for C55H45Au3F3O4P3S: C, 42.82; H, 2.94; S, 2.08.
Found: C, 42.72; H, 2.85; S, 2.15.
O(1)-Au(1)-P(1)
P(1)-Au(1)-Au(3)
P(1)-Au(1)-Au(2)
O(1)-Au(1)-Au(3)a
175.67(13) O(1)-Au(1)-Au(3)
131.44(5) O(1)-Au(1)-Au(2)
138.21(5) Au(3)-Au(1)-Au(2)
71.24(13) P(1)-Au(1)-Au(3)a
44.27(13)
41.29(13)
60.05(2)
110.75(6)
Au(3)-Au(1)-Au(3)a 89.20(3) Au(2)-Au(1)-Au(3)a 109.23(4)
O(1)-Au(2)-P(2)
P(2)-Au(2)-Au(3)
P(2)-Au(2)-Au(1)
O(1)-Au(3)-P(3)
P(3)-Au(3)-Au(1)
P(3)-Au(3)-Au(2)
O(1)-Au(3)-Au(1)a
175.33(14) O(1)-Au(2)-Au(3)
141.43(5) O(1)-Au(2)-Au(1)
137.93(5) Au(3)-Au(2)-Au(1)
175.04(13) O(1)-Au(3)-Au(1)
132.10(5) O(1)-Au(3)-Au(2)
134.72(5) Au(1)-Au(3)-Au(2)
72.48(12) P(3)-Au(3)-Au(1)a
43.21(13)
42.22(12)
58.46(2)
44.20(12)
42.17(12)
61.49(3)
111.95(5)
Au(1)-Au(3)-Au(1)a 90.80(3) Au(2)-Au(3)-Au(1)a 110.36(3)
Au(2)-O(1)-Au(1)
Au(1)-O(1)-Au(3)
96.5(2)
91.5(2)
Au(2)-O(1)-Au(3)
94.6(2)
a Symmetry transformation used to generate equivalent atoms: -x
+ 1, -y + 1, -z + 1.
2θ < 23°). An absorption correction based on ψ scans was applied,
with transmission factors of 0.493-0.981. The structure was solved
by direct methods and refined anisotropically on F2.25 Hydrogen atoms
were included by using a riding model or as rigid methyl groups. The
triflate anion is disordered over two sites. Tables 1 and 2 give
crystallographic data and important bond lengths and angles, respec-
tively.
[{AuP(C6H4OMe-4)3}3(µ3-O)]OTf (7b). Similarly, from the
reaction of (Ph2NH2)OTf (43 mg, 0.13 mmol) and [Au(acac-κC2)-
{P(C6H4OMe-4)3}] (174 mg, 0.27 mmol) in acetone (15 mL) for 0.5
h, 7b was obtained. Yield: 78 mg, 48%. Mp: 175 °C. ΛM ) 93
Ω-1‚cm2‚mol-1 (6.5 × 10-4 mol‚L-1). 1H NMR (300 MHz, CDCl3;
[Au(NH3)2]Cl (8a). [AuCl(tht)] (200 mg, 0.62 mmol) was dissolved
in 15 mL of acetone, and NH3 was bubbled through the solution until
no more white precipitate was formed. The suspension was stirred
for 5 min and filtered, and the white solid was washed with diethyl
ether (2 × 10 mL) and air-dried. Yield: 159 mg, 96%. Mp: 188 °C.
δ): 3.80 (s, 27H, OMe), 6.81 (dd, 18 H, C6H4, 3JHH ) 8.4 Hz, 4JPH
)
1.8 Hz), 7.37 (dd, 18H, C6H4, JPH ) 12.6 Hz). 31P{1H} NMR (121
MHz, CDCl3; δ): 19.27 (s). Anal. Calcd for C64H63Au3F3O13P3S: C,
42.40; H, 3.50; S, 1.77. Found: C, 42.22; H, 3.44; S, 1.76.
3
IR: ν(NH) 3074, 3167, 3224 cm-1 1H NMR (300 MHz, DMSO-d6;
.
δ): 4.626 (s, br, NH3). Anal. Calcd for H6AuClN2: C, 0.00; H, 2.27;
N, 10.51. Found: C, 0.19; H, 2.16; N, 10.29.
[Au(NH3)2]ClO4 (8b). [Au(NH3)2]Cl (8a) (104 mg, 0.4 mmol) was
added to a solution of AgClO4 (89 mg, 0.43 mmol) in acetone (10
mL), and the resulting suspension was stirred for 20 min. AgCl was
Crystal Structure Determination of 7b. A colorless 0.5 × 0.3 ×
0.1 mm tablet of 7b‚Me2CO, obtained by liquid diffusion of Me2CO/
Et2O, was mounted in inert oil on a glass fiber and transferred to a
diffractometer (Siemens P4 with an LT2 low-temperature attachment).
A set of 12 562 reflections (2θmax 50°, 12 039 unique, Rint 0.019) was
collected using Mo KR radiation. Unit cell parameters were determined
from a least-squares fit of 56 accurately centered reflections (10° <
(25) Sheldrick, G. M. SHELXL 93. University of Go¨ttingen, 1993.

Gold(I) Complexes with N-Donor Ligands
Inorganic Chemistry, Vol. 36, No. 20, 1997 4441
Scheme 2. Synthesis of Complexes 4-7
Scheme 1. Synthesis of Complexes 1-3
removed by filtration, the solution was concentrated (2 mL), and di-
ethyl ether (20 mL) was added to precipitate 8b as a white solid.
Yield: 119 mg, 92%. Mp: 184 °C dec. ΛM ) 139 Ω-1‚cm2‚mol-1
(6 × 10-4 mol‚L-1). IR: ν(NH), 3258, 3323 cm-1
.
1H NMR (300
1
°C in CH2Cl2 for 10 min or at -60 °C in THF for 5 min. Upon
addition of diethyl ether, the 31P NMR spectra of the isolated
solids show them both to contain mixtures of the reagents
along with the nitrido complex 3b. Additionally, in the reac-
tion at -60 °C, a small amount of [(AuPR3)3(µ3-O)]+ is
present. The reaction of 2a with [Au(acac-κC2)(PPh3)], 1:1, at
room temperature under nitrogen atmosphere using degassed
CH2Cl2, gives after 10 min of stirring a mixture of the starting
complexes and the oxonium salt [(AuPPh3)3(µ3-O)]ClO4. On
the other hand, the reaction of (NH4)ClO4 with [Au(acac-κC2)-
(PPh3)] (1:3, in THF, 1 h) gives upon concentration and
addition of diethyl ether a solid whose 31P{1H} NMR shows
the presence of 1a, 3a, and [(AuPPh3)3(µ3-O)]ClO4. The species
[(AuPR3)3(NH)]+ is observed in the FAB mass spectrum
of 3b.
MHz, acetone-d6; δ): 4.49 (t, br, NH3 JHN ) 37 Hz). Anal. Calcd
for H6AuClN2O4: C, 0.00; H, 1.83; N, 8.48. Found: C, 0.07; H, 1.66;
N, 8.66.
[Au(NH3)2]OTf (8c). To a suspension of [Au(NH3)2]Cl (8a) (196
mg, 0.74 mmol) in acetone (10 mL) was added TlOTf (260 mg,
0.74 mmol). The suspension was stirred for 10 min, and TlCl was
removed by filtration. The solution was concentrated (2 mL), and
diethyl ether (20 mL) was added to precipitate 8c as a white solid.
Yield: 201 mg, 72%. Mp: 134 °C dec. ΛM ) 132 Ω-1‚cm2‚mol-1
(8 × 10-4 mol‚L-1). IR: ν(NH) 3207, 3306 cm-1
.
1H NMR (300
1
MHz, acetone-d6; δ): 4.53 (t, br, NH3, JHN ) 39 Hz). Anal. Calcd
for CH6AuF3N2O3S: C, 3.16; H, 1.59; N, 7.37; S, 8.44. Found: C,
3.25; H, 1.54; N, 7.05; S, 8.33.
Results and Discussion
Dropwise addition of a tetrahydrofuran solution of [Au(acac-
κC2)(PR3)] (acac ) acetylacetonate; R ) Ph, C6H4OMe-4) to a
suspension of (NH4)ClO4 in the same solvent (molar ratio 1:1.1)
gives [Au(NH3)(PR3)]ClO4 [R ) Ph (1a), C6H4OMe-4 (1b)]
(see Scheme 1). If the order of addition of reagents is reversed
(when R ) C6H4OMe-4), a mixture containing 1b, [(AuPR3)2-
(µ2-NH2)]ClO4 (2b), [(AuPR3)4(µ4-N)]ClO4 (3b), and [Au(PR3)2]-
ClO4 (by 31P NMR) is obtained.
Whereas the complex [(AuPR3)2(µ2-NH2)]ClO4 [R )
C6H4OMe-4 (2b)] can be obtained by dropwise addition of a
dichloromethane solution of [Au(acac-κC2)(PR3)] to a solution
of [Au(NH3)(PR3)]ClO4 (1b) in the same solvent, its analogue
with R ) Ph (2a) must be prepared under a nitrogen atmosphere
using dry solvents. These reactions have been followed in
CDCl3 by 31P NMR spectroscopy at room temperature, proving
that complexes 2a,b are immediately formed. However, 2b
decomposes in solution to give the nitrido complex 3b as the
only phosphorus-containing compound, which explains the fact
that NMR data and FAB mass spectra of analytically pure
samples of 2b always show the presence of small amounts of
3b. On the other hand, 2a is stable for at least 3 h, provided
the solvent is dry. Otherwise, formation of the oxonium salt
[{AuPPh3}3(µ3-O)]ClO4 is immediately observed. An attempt
to prepare 2a by reacting [Au(acac-κC2)(PPh3)] and (NH4)ClO4,
2:1 in THF, led to a mixture containing 1a and [(AuPPh3)4-
(µ4-N)]ClO4 (3a) along with the oxonium salt [(AuPPh3)3-
(µ3-O)]ClO4.
The syntheses of the nitrido complexes [(AuPR3)4(µ4-N)]ClO4
[R ) Ph (3a), C6H4OMe-4 (3b)] are easily achieved by reacting
(NH4)ClO4 with [Au(acac-κC2)(PR3)] in a 1:4 or 1:5 molar ratio
(see Scheme 1). Our method is simpler and gives a higher
yield than those previously reported for the two tetraaurated
compounds [(AuL)4(µ4-N)]BF4 (L ) PPh3, PMe3), prepared
by reacting [(AuL)3(µ3-O)]BF4 with NH3, (Me3Si)2NH, or
[(Me3PAu)3(µ3-NSiMe3)]+.6,8 While in the 31P NMR of 3a a
poorly defined triplet is observed due to 31P-14N coupling, in
the spectrum of 3b a singlet is observed.
Similarly, the reactions of [Au(acac-κC2)(PPh3)] with the
ammonium salts (NH3R′)OTf (1:1) (R′ ) Me, C6H4NO2-4; OTf
) CF3SO3) (1:1) give the complexes [Au(NH2R′)(PR3)]OTf
[R′ ) Me (4), C6H4NO2-4 (5)] (Scheme 2). The reaction of
[Au(acac-κC2)(PPh3)] with [H3N(CH2)2NH2]OTf, which was
intended to produce [(AuPPh3){NH2(CH2)2NH2}]OTf, gave
instead the dinuclear complex [(AuPPh3)2{µ2-H2N(CH2)2NH2}]-
(OTf)2 (6) and NH2(CH2)2NH2. 6 can also be obtained, though
in lower yield, by reacting [Au(acac-κC2)(PPh3)] with [H3N(CH2)2-
NH3](OTf)2, 2:1. While there are a few reported [Au(NH2R′)-
(PR3)]+ complexes [R ) Me, R′ ) tBu, PhCH2;6 R ) Ph, R′ )
C6H4NO2-2, C6H4OMe-41], complex 6 is the first dinuclear
species of this type. A family of polyaurated diamines
[(AuPPh3)3N-X-N(AuPPh3)]2+ [X ) (CH2)2 and 1,4-, 1,3-, and
1,2-C6H4],26 dendritic amines,9 and mixed dinuclear complexes
[RAu{H2N(CH2)xNH2}AuL]n+ [n ) 0, R ) C6F5, L ) Cl, C6F5,
Various attempts to prepare the imido complexes [(AuPR3)3-
(µ3-NH)]ClO4 proved unsuccessful. We studied the reactions
of 2b and [Au(acac-κC2)(PR3)] (R ) C6H4OMe-4), 1:1, at 0
(26) Grohmann, A.; Schmidbaur, H. Inorg. Chem. 1992, 31, 3378.

4442 Inorganic Chemistry, Vol. 36, No. 20, 1997
Scheme 3. Synthesis of Complexes 8a-c
Vicente et al.
x ) 2, 3; n ) 1, R ) C6F5, X ) PPh3, x ) 2]27 have also been
reported.
We recently reported the synthesis of other monoaurated
ammonium salts [Au(L)(PPh3)]+ (L ) primary, secondary, or
tertiary amine).1 For primary and secondary amines, this study
showed that the result depends on the nature of the solvent.
The desired monoaurated ammonium salts could only be
prepared in diethyl ether, in which they are insoluble. The
failure to prepare such complexes in acetone was attributed to
the fact that the corresponding acetone-soluble complexes
[Au(NHnR3-n)(PPh3)]+ (n ) 1, 2) would react further with [Au-
(acac-κC2)PPh3)] to give di- and triaurated ammonium salts.
I.e.: [(AuL)(NHnR3-n)]+ + [Au(acac-κC2)L] f [(AuL)2-
(µ2-NHn-1R3-n)]+; [(AuL)2(µ2-NHn-1R3-n)]+ + [Au(acac-
κC2)L] f [(AuL)3(µ3-NHn-2R3-n)]+. To prove this hy-
pothesis, and because complexes of the type [(AuL)2(µ2-NR2)]X
are very rare,4-7 we reacted [Au(acac-κC2)(PR3)] (R ) Ph,
C6H4OMe-4) with (R′2NH2)OTf (R′ ) Ph, Et) (2:1) in ace-
tone. However, the complexes [{AuPR3}3(µ3-O)]OTf [R ) Ph
(7a), C6H4OMe-4 (7b)] were obtained, certainly as a result of
the hydrolysis of the desired [(AuPR3)2(µ2-NR′2)]+ complexes
(Scheme 2). Similar behavior was previously observed for [Au-
(PPh3)(qncd)]BF4, which in the presence of traces of water gives
quinuclidinium and oxonium salts.10 [(AuPR3)3(µ3-O)]X salts
are known for a variety of phosphines and anions, although not
with P(C6H4OMe-4)3 or with OTf.7,28-33 They are usually
prepared from coordinatively unsaturated R3PAu+ cations in
alkaline or acid media with better yields than obtained by our
method. Recently, [(LAu)4(µ4-O)]2+ (L ) PR3, R ) Ph, o-tolyl)
complexes have been reported.34
Recently, Mingos presented a preliminary report of the
synthesis of several [Au(NH3)2]X salts by bubbling ammonia
through a solution of [Au(NCPh)2]X (X ) BF4, SbF6; yield
approximately 90%) or by introducing NH3 into a solution of
[AuBr2]- (yield not specified but lower than those of the other
salts).20 Since one of us prepared [AuCl(tht)] (tht ) tetrahy-
drothiophene) and showed for the first time its synthetic utility,35
most gold chemists have used it as starting material.36 There-
fore, it seems interesting to show that it can also be used to
prepare [Au(NH3)2]+, rather than the less familiar [Au(NCPh)2]+
complex.21,33,37 In fact, bubbling NH3 through a solution of
[AuCl(tht)] (tht ) tetrahydrothiophene) in acetone precipitates
the complex [Au(NH3)2]Cl (8a) quantitatively (Scheme 3). Other
salts could be prepared by reacting 8a with the corresponding
silver or thallium salt. Thus, by reaction of 8a with AgClO4 or
Figure 1. ORTEP diagram showing the labeling scheme of the
asymmetric unit of 7b‚Me2CO. H atoms are omitted for clarity.
TlOTf, and after removal of AgCl or TlCl, [Au(NH3)2]X [X )
ClO4 (8b) or OTf (8c)] can be isolated in high (72-92%) yield.
These two salts behave in solution as 1:1 electrolytes. The
insolubility of 8a precludes conductivity measurements. We
have formulated it according to the structure of its bromide
analogue.20
Crystal Structure of 7b. The crystal structure of 7b‚
Me2CO has been determined (see Figure 1). Like all previous
crystal structures of trigold oxonium compounds,29-32 it shows
a nearly trigonal pyramidal array of three gold atoms and one
oxygen atom with O-Au-P bond angles of ca. 175°. The
Au-O [2.026(5)-2.066(4) Å], Au-P [2.210(2)-2.222(2) Å],
and Au‚‚‚Au distances [2.9585(7)-3.0505(14) Å] and the
Au-O-Au bond angles [91.5(2)-96.5(2)°] are in the ranges
found in one crystalline form of its homologue with PPh3.30
The [(AuPR3)3(µ3-O)]+ cations are combined via interionic Au4
(36) For some recent examples, see: Albano, V. G.; Busetto, L.; Cassani,
M. C.; Sabatino, P.; Schmitz, A.; Zanotti, V. J. Chem. Soc., Dalton
Trans. 1995, 2087. Assefa, Z.; McBurnett, B. G.; Staples, R. J.;
Fackler, J. P., Jr. Inorg. Chem. 1995, 34, 4965. Bonasia, P. J.;
Gindelberger, D. E.; Arnold, J. Inorg. Chem. 1993, 32, 5126. Chiffey,
A. F.; Evans, J.; Levason, W.; Webster, M. Polyhedron 1996, 15, 591.
Coco, S.; Espinet, P.; Falagan, S.; Mart´ın-Alvarez, J. M. New J. Chem.
1995, 19, 959. Fornie´s, J.; Navarro, R.; Urriolabeitia, E. P. J.
Organomet. Chem. 1993, 452, 241. Gibson, A. M.; Reid, G. J. Chem.
Soc., Dalton Trans. 1996, 1267. Gimeno, M. C.; Jambrina, E.; Laguna,
A.; Laguna, M.; Murray, H. H.; Terroba, R. Inorg. Chim. Acta 1996,
249, 69. Alvarez, S.; Rossell, O.; Seco, M.; Valls, J.; Pellinghelli, M.
A.; Tiripicchio, A. Organometallics 1991, 10, 2309. Arena, C. G.;
Drommi, D.; Faraone, F.; Lanfranchi, M.; Nicolo, F.; Tiripicchio, A.
Organometallics 1996, 15, 3170. Jeffery, J. C.; Jelliss, P. A.; Stone,
F. G. A. Organometallics 1994, 13, 2651. Liu, L. K.; Luh, L. S.; Wen,
Y. S.; Eke, U. B.; Mesubi, M. A. Organometallics 1995, 14, 4474.
Neda, I.; Fischer, A.; Kaukorat, T.; Jones, P. G.; Schmutzler, R. Chem.
Ber. 1994, 127, 1579. Raubenheimer, H. G.; Lindeque, L.; Cronje, S.
J. Organomet. Chem. 1996, 511, 177. Riera, V.; Ruiz, M. A.;
Tiripicchio, A.; Tiripicchio-Camellini, M. Organometallics 1993, 12,
2962. Salter, I. D.; Sik, V.; Williams, S. A.; Adatia, T. J. Chem. Soc.,
Dalton Trans. 1996, 643. Slany, M.; Bardaji, M.; Casanove, M. J.;
Caminade, A. M.; Majoral, J. P.; Chaudret, B. J. Am. Chem. Soc. 1995,
117, 9764. Slawin, A. M. Z.; Smith, M. B.; Woollins, J. D. J. Chem.
Soc., Dalton Trans. 1996, 1283. Zeller, E.; Schier, A.; Schmidbaur,
H. Z. Naturforsch., B 1994, 49, 1243. Ahrland, S.; Dreisch, K.; Noren,
B.; Oskarsson, A. Mater. Chem. Phys. 1993, 35, 281. Bautista, M.
T.; White, P. S.; Schauer, C. K. J. Am. Chem. Soc. 1994, 116, 2143.
Viotte, M.; Gautheron, B.; Kubicki, M. M.; Nifant’ev, I. E.; Fricker,
S. P. Met.-Based Drugs 1995, 2, 311.
(27) Uso´n, R.; Laguna, A.; Villacampa, M. D. Inorg. Chim. Acta 1984,
81, 25.
(28) Schmidbaur, H.; Kolb, A.; Zeller, E.; Schier, A.; Beruda, H. Z. Anorg.
Allg. Chem. 1993, 619, 1575.
(29) Nesmeyanov, A. N.; Perevalova, E. G.; Struchkov, Y. T.; Antipin,
M. Y.; Grandberg, K. I.; Dyadchenko, V. P. J. Organomet. Chem.
1980, 201, 343.
(30) Yang, Y.; Ramamoorthy, V.; Sharp, P. R. Inorg. Chem. 1993, 32,
1946.
(31) Angermaier, K.; Schmidbaur, H. Inorg. Chem. 1994, 33, 2069.
(32) Angermaier, K.; Schmidbaur, H. Acta Crystallogr. 1995, C51, 1793.
(33) Mingos, D. M. P.; Yau, J. J. Organomet. Chem. 1994, 479, C16.
(34) Schmidbaur, H.; Hofreiter, S.; Paul, M. Nature 1995, 377, 503.
(35) Uso´n, R.; Laguna, A.; Vicente, J. J. Chem. Soc., Chem. Commun.
1976, 353. Uso´n, R.; Laguna, A.; Vicente, J. J. Organomet. Chem.
1977, 131, 471.
(37) Kissner, R.; Latal, P.; Geier, G. J. Chem. Soc., Chem. Commun. 1993,
136.

Gold(I) Complexes with N-Donor Ligands
Inorganic Chemistry, Vol. 36, No. 20, 1997 4443
Chart 1
structures of complexes with PPh2Me and PPh3 (see Chart 1).29,30
Other trigold oxonium compounds with bulkier phosphines (R
) o-tolyl,30 iPr32) have been isolated as monomeric cations
without intermolecular Au‚‚‚Au bonding, whereas in the
analogue with the smallest tertiary phosphine, PMe3, the Au4
core is tetrahedral (see Chart 1).31
Intermolecular bond distances Au(1)-Au(3#) in 7b [3.0919-
(9) Å] are significantly longer than the intramolecular
Au‚‚‚Au. This represents a difference from all other such
complexes, in which inter- and intramolecular contacts are
similar.29-31 However, the intermolecular Au‚‚‚Au bond dis-
tances in 7b are some of the shortest reported [cf. 3.162(6)29
and 3.1332(9)30 for L ) PPh3, 3.220(1)-3.312 Å for L )
PMe3,31 but 3.0616(12) Å for L ) PPh2Me30].
Acknowledgment. We thank the Direccio´n General de
Investigacio´n Cient´ıfica y Te´cnica (Project PB92-0982-C) and
the Fonds der Chemischen Industrie for financial support. R.G.
and M.C.R.d.A. thank the Ministerio de Educacio´n y Ciencia
(Spain) for a Grant and for a Contract, respectively.
Supporting Information Available: An X-ray crystallographic file,
in CIF format, for the structure of 7b‚Me2CO is available on the Internet
only. Access information is given on any current masthead page.
aggregations into centrosymmetric dimers. The gold atoms of
the dimer form a six-membered ring with a chair conformation.
This type of intermolecular bonding is also found in the
IC970225J