Inorg. Chem. 2006, 45, 1888−1890
Gold(I)
η
2-Arene Complexes
Qing-Shan Li, Chong-Qing Wan, Ru-Yi Zou, Feng-Bo Xu,* Hai-Bin Song, Xiang-Jian Wan, and
Zheng-Zhi Zhang*
State Key Laboratory of Elemento-Organic Chemistry, Nankai UniVersity, Tianjin 300071, China
Received October 27, 2005
Scheme 1
The reaction of 9-{[N-n-propyl-N-(diphenylphosphino)amino]methyl}-
anthracene (1) with Au(SMe2)Cl yields complex 2 with an arm-
opening configuration. The latter is treated with AgClO4 to form
complex 4 and then respectively reacted with acetonitrile, pyridine,
and triphenylphosphine sulfide to afford novel gold(I)
complexes 3a c, which have arm-closing configurations and feeble
η
2-arene
−
or weak fluorescence emissions. The observation can be attributed
to charge transfer from the anthracene unit to the Au+ ion. When
the solution of 3a or 4 in CH2Cl2 was added with 1 equiv of Ph3P,
complex 5 with the arm-opening configuration was formed and
strong emission was restored.
The molecular structures of complexes 2 and 3a-c have
been determined by X-ray diffraction analysis.4,5 As shown
in Figure 1, the linear two-coordinated Au unit Cl(1)-
Au(1)-P(1) (178.37°) is perpendicular to the anthracene ring
in 2 (an arm-opening configuration). When the Cl atom is
substituted by a CH3CN, pyridine, or Ph3PdS molecule in
elimination and coordination reactions, similar linear two-
coordinated Au units P(1)-Au(1)-N(2) (179.59°; 3a), P(1)-
Au(1)-N(2) (177.07°; 3b), and P(1)-Au(1)-S(1) (172.0°;
3c) fold toward the anthracene planes (arm-closing configu-
rations) (Figures 2 and 3 and the Supporting Information).
The angles Au(1)-P(1)-N(1) are 111.06° (3a), 112.54° (3b),
As far as the group 11 metal-arene π complex is
concerned, there are numerous η2-bonding complexes be-
tween Ag+ and the aromatic compound1 and a few of the
Cu+ analogues;2 surprisingly, no gold(1+) η2-arene complex
is reported. In 2003, we presented a new molecular design
and gave the first gold(I) arene complex,3 which is formed
by the reaction of chelated diphosphine ligand 9,10-bis{[N-
n-propyl-N-(diphenyphosphino)amino]methyl}anthracene with
the Au+ ion and adopts a η6-coordination mode.
Herein we report some novel gold(I) η2-arene complexes,
their substitution reaction, and molecular responsive fluo-
rescence spectral variation. In the first place, as shown in
Scheme 1, 9-{[N-n-propyl-N-(diphenylphosphino)amino]-
methyl}anthracene (1) was prepared by the reaction of 9-[(N-
propylamino)methyl)]anthracene with Ph2PCl. Then, the
reaction of 1 with a stoichiometric amount of Au(SMe2)Cl
gave complex 2, which converted to complexes 3a-c by
treatment with AgClO4 and reaction with acetonitrile, pyri-
dine, and triphenylphosphine sulfide, respectively.
(4) Crystal data for 2: C30H28AuClNP, M ) 665.92, monoclinic, space
group P2(1)/c, a ) 9.595(3) Å, b ) 16.081(5) Å, c ) 17.189(5) Å,
R ) 90°, â ) 92.575(5)°, γ ) 90°, V ) 2649.4(14) Å3, Z ) 4, Dc )
1.669 g cm-3, F(000) ) 1304, µ(Mo KR) ) 5.733 cm-1, T ) 293(2)
K, 5415 variables refined with 15 061 reflections with I > 2σ(I) to
R ) 0.0511.
(5) Crystal data for 3a: C32H31AuClN2O4P, M ) 770.97, triclinic, space
group P1, a ) 9.419(3) Å, b ) 12.900(4) Å, c ) 13.893(4) Å, R )
110.198(4)°, â ) 104.902(5)°, γ ) 95.536(4)°, V ) 1498.8(7) Å3,
Z ) 2, Dc ) 1.708 g cm-3, F(000) ) 760, µ(Mo KR) ) 5.090 cm-1
,
T ) 293(2) K, 6964 variables refined with 9710 reflections with I >
2σ(I) to R ) 0.0415. Crystal data for 3b: C35H33AuClN2O4P, M )
809.02, orthorhombic, space group Pna2(1), a ) 10.2098(10) Å, b )
23.903(2) Å, c ) 13.1372(13) Å, R ) 90°, â ) 90°, γ ) 90°,
V ) 3206.1(5) Å3, Z ) 4, Dc ) 1.676 g cm-3, F(000) ) 1600,
µ(Mo KR) ) 4.763 cm-1, T ) 293(2) K, 7598 variables refined with
20 644 reflections with I > 2σ(I) to R ) 0.0317. Crystal data for 3c:
C48H43AuClNO4P2S, M ) 1024.25, monoclinic, space group P2(1)/c,
a ) 13.248(3) Å, b ) 16.329(3) Å, c ) 20.240(4) Å, R ) 90°, â )
* To whom correspondence should be addressed. E-mail: zzzhang@
nankai.edu.cn (Z.-Z.Z.).
(1) (a) Munakata, M.; Wu, L. P.; Ning, G. L. Coord. Chem. ReV. 2000,
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Chem. 2000, 39, 5707-5716.
(2) (a) Turner, R. W.; Amma, E. L. J. Am. Chem. Soc. 1966, 88, 1877-
1882. (b) Dines, M. B.; Bird, P. H. J. Chem. Soc., Chem. Commun.
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2843.
90.25(3)°, γ ) 90°, V ) 4378.7(15) Å3, Z ) 4, Dc ) 1.554 g cm-3
,
F(000) ) 2048, µ(Mo KR) ) 3.586 cm-1, T ) 293(2) K, 7652
variables refined with 20 309 reflections with I > 2σ(I) to R ) 0.1154.
Diffractometer: Bruker Smart 1000 CCD diffractometer employing
graphite-monochromatized Mo KR radiation (λ ) 0.710 73 Å).
(3) Xu, F. B.; Li, Q. S.; Wu, L. Z.; Leng, X. B.; Li, Z. C.; Zeng, X. S.;
Chow, Y. L.; Zhang, Z. Z. Organometallics 2003, 22, 633-640.
1888 Inorganic Chemistry, Vol. 45, No. 5, 2006
10.1021/ic051869r CCC: $33.50
© 2006 American Chemical Society
Published on Web 02/08/2006