New ylide-, alkynyl-, and mixed alkynyl/ylide-gold(I) complexes

Article abstract of DOI:10.1021/om020753p

Reactions of AuCl(tht) (tht = tetrahydrothiophene) with various ylides in equimolar amounts give the complexes [AuCl(ylide)]X_n (n = 0, ylide = C(PPh₃)₂ (la), 4-MeC₆H₄SO₂CHPPh₃ (1b); n = 1, X = TfO, ylide = [HC(PPh₃)₂]⁺ (2)) and [(AuCl)₂{μ-C(PPh₃)₂}] (3) when using a 2:1 molar ratio. The complex la reacts (i) with Tl(acac) to give [Au(acac){C(PPh₃)₂}] (4) and (ii) with terminal alkynes (with or without added Et₃N) to give [HC(PPh₃)₂] [Au(C=CC₆H₄R-4)Cl] (R = H (5a), CN (5b), OMe (5c), NO2 (5d)) instead of the desired complexes [Au(C=CC₆H₄R-4){C{PPh₃}₂}]. These complexes (R = H (6a), CN (6b), OMe (6c), NO₂ (6d), C≡CPh (6e)) were prepared by the reaction of [Au(acac){C(PPh₃)₂}] (4) with a large excess of alkynes (ca. 1:25-30). Complex 1b reacts with terminal alkynes in the presence of Et₃N differently from 1a, giving the complexes [Au(C≡CC₆H₄R-4){CH(PPh₃){S(O)₂ C₆H₄Me-4}}](R = H (7a), NC (7b), OMe (7c), NO2 (7d), C≡CPh (7e)). The reaction of PPN[Au(acac)₂] with the phosphonium salt [H₂C(PPh₃)₂](TfO)₂ or [4-MeC₆H₄S(O)₂CH₂PPh₃]TfO in 1:2 stoichiometry afforded the cationic complex [Au(ylide)₂](TfO)_n, where the ylide is [HC(PPh₃)₂]^- (n = 3, 8a) or 4-MeC₆H₄S(O)₂CHPPh₃ (n = 1, 8b), respectively. The crystal structures of [4-MeC₆H₄S(O)₂CH₂PPh₃]TfO , 1b-0.5CH₂Cl₂, 3.3CH₂Cl₂, 5a, 5c, 6d·THF, and 8b have been determined.

Full text of DOI:10.1021/om020753p

Organometallics 2002, 21, 5887-5900
5887
New Ylid e-, Alk yn yl-, a n d Mixed Alk yn yl/Ylid e-Gold (I)
Com p lexes
J ose´ Vicente*,† and Anshu R. Singhal‡
Grupo de Quı´mica Organometa´lica, Departamento de Quı´mica Inorga´nica,
Facultad de Quı´mica, Universidad de Murcia, Apartado 4021, Murcia, E-30071 Spain
Peter G. J ones§
Institut fu¨r Anorganische und Analytische Chemie, Technische Universita¨t Braunschweig,
Postfach 3329, Braunschweig, Germany
Received September 11, 2002
Reactions of AuCl(tht) (tht ) tetrahydrothiophene) with various ylides in equimolar
amounts give the complexes [AuCl(ylide)]Xn (n ) 0, ylide ) C(PPh3)2 (1a ), 4-MeC6H4SO2-
CHPPh3 (1b); n ) 1, X ) TfO, ylide ) [HC(PPh3)2]+ (2)) and [(AuCl)2{µ-C(PPh3)2}] (3) when
using a 2:1 molar ratio. The complex 1a reacts (i) with Tl(acac) to give [Au(acac){C(PPh3)2}]
(4) and (ii) with terminal alkynes (with or without added Et3N) to give [HC(PPh3)2][Au-
(CtCC6H4R-4)Cl] (R ) H (5a ), CN (5b), OMe (5c), NO2 (5d )) instead of the desired complexes
[Au(CtCC6H4R-4){C{PPh3}2}]. These complexes (R ) H (6a ), CN (6b), OMe (6c), NO2 (6d ),
CtCPh (6e)) were prepared by the reaction of [Au(acac){C(PPh3)2}] (4) with a large excess
of alkynes (ca. 1:25-30). Complex 1b reacts with terminal alkynes in the presence of Et3N
differently from 1a , giving the complexes [Au(CtCC6H4R-4){CH(PPh3){S(O)2C6H4Me-4}}]
(R ) H (7a ), NC (7b), OMe (7c), NO2 (7d ), CtCPh (7e)). The reaction of PPN[Au(acac)2]
with the phosphonium salt [H2C(PPh3)2](TfO)2 or [4-MeC6H4S(O)2CH2PPh3]TfO in 1:2
stoichiometry afforded the cationic complex [Au(ylide)2](TfO)n, where the ylide is [HC(PPh3)2]+
(n ) 3, 8a ) or 4-MeC6H4S(O)2CHPPh3 (n ) 1, 8b), respectively. The crystal structures of
[4-MeC6H4S(O)2CH2PPh3]TfO, 1b‚0.5CH2Cl2, 3‚3CH2Cl2, 5a , 5c, 6d ‚THF, and 8b have been
determined.
In tr od u ction
catalysts.7 Recent reports have detailed alkane oxygen-
ation8 and hydrosilylation reactions.9 Many gold(I)
complexes show Au‚‚‚Au interactions that are weaker
than normal covalent bonds but stronger than van der
Waals forces. These interactions are termed auro-
philic10,11 and determine the supramolecular structure
of many gold(I) complexes as well as the formation of
rare hypercoordinate complexes;12,13 they are partially
responsible for the interesting photophysical properties
of many of these compounds.14-16
Gold(I) complexes are interesting from both theoreti-
cal and applied standpoints. Thus, in addition to the
well-known applications as antiarthritic agents,1 other
medicinal applications have been reported, extending
from chemotherapy2,3 to treatments of tropical diseases,4
thrombosis,5 or cancer.6 An increasing number of pub-
lications have documented the potential of soluble gold
† E-mail: jvs@um.es. Web: http://www.scc.um.es/gi/gqo/.
‡ On leave from the Novel Materials and Structural Chemistry
Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400 085
India. E-mail: ansing@magnum.barc.ernet.in.
(7) Thompson, D. T. Gold Bull. 2001, 34, 134.
(8) Shulpin, G. B.; Shilov, A. E.; Sussfink, G. Tetrahedron Lett. 2001,
42, 7253.
(9) Ito, H.; Yajima, T.; Tateiwa, J .; Hosomi, A. Chem. Commun.
2000, 981.
(10) Vicente, J .; Chicote, M. T.; Saura-Llamas, I.; Lagunas, M. C.;
Ram´ırez de Arellano, M. C.; Gonza´lez-Herrero, P.; Abrisqueta, M. D.;
Guerrero, R. In Metal Clusters in Chemistry; Braunstein, P., Oro, L.
A., Raithby, P. R., Eds., Wiley-VCH: Weinheim, Germany, 1999; Vol.
1, p 493.
(11) Scherbaum, F.; Grohmann, A.; Huber, B.; Kru¨ger, C.; Schmid-
baur, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 1544. Leznoff, D. B.;
Xue, B. Y.; Batchelor, R. J .; Einstein, F. W. B.; Patrick, B. O. Inorg.
Chem. 2001, 40, 6026. Schmidbaur, H. Nature 2001, 413, 31. Brandys,
M. C.; Puddephatt, R. J . Chem. Commun. 2001, 1280. Hamel, A.;
Mitzel, N. W.; Schmidbaur, H. J . Am. Chem. Soc. 2001, 123, 5106.
Van Calcar, P. M.; Olmstead, M. M.; Balch, A. L. J . Chem. Soc., Chem.
Commun. 1995, 1773. J iang, F. L.; Olmstead, M. M.; Balch, A. L. J .
Chem. Soc., Dalton Trans. 2000, 4098. J ones, P. G.; Ahrens, B. New
J . Chem. 1998, 22, 1041.
§ E-mail: jones@xray36.anchem.nat.tu-bs.de.
(1) Best, S. L.; Sadler, P. J . Gold Bull. 1996, 29, 87. Fricker, S. P.
Gold Bull. 1996, 29, 53. Sadler, P. J . Adv. Inorg. Chem. 1991, 36, 1.
Guo, Z. J .; Sadler, P. J . Angew. Chem., Int. Ed. 1999, 38, 1513.
(2) Guo, Z. J .; Sadler, P. J . Adv. Inorg. Chem. 2000, 49, 183.
(3) Shaw, C. F. Chem. Rev. 1999, 99, 2589.
(4) Navarro, M.; Cisneros-Fajardo, E. J .; Lehmann, T.; Sa´nchez-
Delgado, R. A.; Atencio, R.; Silva, P.; Lira, R.; Urbina, J . A. Inorg.
Chem. 2001, 40, 6879. Sanchez-Delgado, R. A.; Navarro, M.; Lazardi,
K.; Atencio, R.; Capparelli, M.; Vargas, F.; Urbina, J . A.; Bouillez, A.;
Noels, A. F.; Masi, D. Inorg. Chim. Acta 1998, 276, 528.
(5) Kean, W. F.; Lock, C. J . L.; Somers, D.; Rischke, J .; Nablo, L.;
Kassam, Y. B.; Hogan, M. G.; Buchanan, W. W.; Howard-Lock, H. E.
J . Pharm. Sci. 1991, 80, 113.
(6) Song, Y. C.; Vittal, J . J .; Srinivasan, N.; Chan, S. H.; Leung, P.
H. Tetrahedron: Asymmetry 1999, 10, 1433. Berners-Price, S. J .;
Frenkiel, T. A.; Ranford, J . D.; Sadler, P. J . J . Chem. Soc., Dalton
Trans. 1992, 2137. Shi, J . C.; Chen, L. J .; Huang, X. Y.; Wu, D. X.;
Kang, B. S. J . Organomet. Chem. 1997, 535, 17. Viotte, M.; Gautheron,
B.; Kubicki, M. M.; Nifant’ev, I. E.; Fricker, S. P. Met.-Based Drugs
1995, 2, 311. Mirabelli, C. K.; J ohnson, R. K.; Sung, C. M.; Faucette,
L.; Muirhead, K.; Crooke, S. T. Cancer Res. 1985, 45, 32.
(12) Schmidbaur, H. Chem. Soc. Rev. 1995, 391.
(13) Vicente, J .; Chicote, M. T.; Guerrero, R.; J ones, P. G. J . Am.
Chem. Soc. 1996, 118, 699.
10.1021/om020753p CCC: $22.00 © 2002 American Chemical Society
Publication on Web 11/23/2002

5888 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
The preference of gold(I) for linear dicoordination,
together with the linearity of the CtC bond in alkynyl
ligands, makes alkynylgold(I) complexes attractive can-
didates for the design of linear-chain metal-containing
polymers with extended electronic conjugation along the
backbone.17 The rapidly growing interest in alkynylgold-
(I) complexes is associated with the expectation that
these electronically flexible rigid-rod polymers might
exhibit interesting properties either difficult or impos-
sible to achieve with conventional organic polymers.
Thus, some alkynyl gold(I) complexes have liquid crys-
talline properties,18 nonlinear optical behavior,19,20 or
interesting photophysical or photochemical proper-
ies.14,21 The objective of the present work was to prepare
alkynylgold(I) complexes containing ylides to study their
NLO properties. Although they did not show such
properties, the results were nonetheless remarkable, as
presented below.
The only previously known gold complex with the
diylide C(PPh3)2 is [AuCl{C(PPh3)2}] (1a ),29 preliminar-
ily reported by Schmidbaur and obtained by reacting
C(PPh3)2 with [AuCl(CO)]. In this work, we report a
different way to synthesize 1a and other complexes with
this ligand, including the unusual dinuclear complex
[(AuCl)2{µ-{C(PPh3)2}}] (3), the first acetylacetonato-
ylide gold complex, [Au(acac){C(PPh3)2}] (4), and the
family of alkyne complexes [Au(CtCR){C(PPh3)2}] (6).
We have previously reported some complexes containing
bridging ylides, but in contrast to 3, they are cationic
species of the general formula [(AuPR3)2{µ-{CR′-
(PR3)}}]+.30-33 Related to 3 are the complexes [(AuMe)2-
{µ-C(PMe3)2}]34 and [(AuPPh3)2{µ-C(PMePh2)2}]2+ 35
.
The number of complexes with the ligand C(PPh3)2
is very limited, despite several attempts to coordinate
it to low- and high-valent transition elements. Thus,
reactions with [MBr(CO)5] (M ) Mn, Re), [Fe(CO)5], [Fe-
(CS)(CO)4], and [W(CO)6] led to the Wittig products
[MBr(CtCPPh3)(CO)4],36 [Fe(CtCPPh3)(CO)4], and [Fe3-
(CtCPPh3)(CO)9]37 and the hydrolysis product [W(CO)5-
(OPPh2CHPPh3)],38 respectively. Similarly, all attempts
to prepare Pt(IV) complexes were unsuccessful. Thus,
the reaction of [PtMe3I] with C(PPh3)2 was sluggish and
incomplete and, in the presence of AgPF6 or AgOSO2-
CF3, led to methane, [HC(PPh3)2]+, and Pt(II) complexes
containing derivatives of C(PPh3)2, depending on the
molar ratio of the reagents. Likewise, reduction of Cu-
(II) to Cu(I) was observed when C(PPh3)2 was reacted
with CuCl2, giving [ClC(PPh3)2][CuCl2].29 Despite these
difficulties, some complexes have been isolated: for
example, [W(CO)5{C(PPh3)2}],39 [Ni(CO)n{C(PPh3)2}] (n
) 3,36,40 240), [MX{C(PPh3)2}] (M ) Cu, Ag, Au, X ) Cl,
Phosphorus ylides are an interesting group of ligands,
and their coordination chemistry with transition and
nontransition elements has been thoroughly re-
viewed.22-24 A large number of gold(I) complexes with
phosphorus ylides are known.25-28
(14) Che, C. M.; Chao, H. Y.; Miskowski, V. M.; Li, Y. Q.; Cheung,
K. K. J . Am. Chem. Soc. 2001, 123, 4985.
(15) Rawashdeh-Omary, M. A.; Omary, M. A.; Fackler, J . P.; Galassi,
R.; Pietroni, B. R.; Burini, A. J . Am. Chem. Soc. 2001, 123, 9689.
(16) Vickery, J . C.; Olmstead, M. M.; Fung, E. Y.; Balch, A. L. Angew.
Chem., Int. Ed. Engl. 1997, 36, 1179. Gade, L. H. Angew. Chem., Int.
Ed. Engl. 1997, 36, 1171. Vogler, A.; Kunkely, H. Coord. Chem. Rev.
2001, 219, 489. Brandys, M. C.; Puddephatt, R. J . J . Am. Chem. Soc.
2001, 123, 4839. Fu, W. F.; Chan, K. C.; Cheung, K. K.; Che, C. M.
Chem. Eur. J . 2001, 7, 4656. Yam, V. W. W.; Chan, C. L.; Li, C. K.;
Wong, K. M. C. Coord. Chem. Rev. 2001, 216, 173. Burini, A.; Fackler,
J . P.; Galassi, R.; Grant, T. A.; Omary, M. A.; Rawashdehomary, M.
A.; Pietroni, B. R.; Staples, R. J . J . Am. Chem. Soc. 2000, 122, 11264.
Fernandez, E. J .; Gimeno, M. C.; Laguna, A.; Lopez de Luzuriaga, J .
M.; Monge, M.; Pyykko, P.; Sundholm, D. J . Am. Chem. Soc. 2000,
122, 7287. Calhorda, M. J .; Crespo, O.; Gimeno, M. C.; J ones, P. G.;
Laguna, A.; Lopez de Luzuriaga, J . M.; Perez, J . L.; Ramon, M. A.;
Veiros, L. F. Inorg. Chem. 2000, 39, 4280. Yam, V. W. W.; Lo, K. K.
W. Chem. Soc. Rev. 1999, 28, 323.
(17) Irwin, M. J .; J ia, G. C.; Payne, N. C.; Puddephatt, R. J .
Organometallics 1996, 15, 51. Irwin, M. J .; Vittal, J . J .; Puddephatt,
R. J . Organometallics 1997, 16, 3541. J ia, G. C.; Puddephatt, R. J .;
Vittal, J . J .; Payne, N. C. Organometallics 1993, 12, 263. J ia, G. C.;
Puddephatt, R. J .; Scott, J . D.; Vittal, J . J . Organometallics 1993, 12,
3565. J ia, G. C.; Payne, N. C.; Vittal, J . J .; Puddephatt, R. J .
Organometallics 1993, 12, 4771. Bruce, M. I.; Hall, B. C.; Skelton, B.
W.; Smith, M. E.; White, A. H. J . Chem. Soc., Dalton Trans. 2002,
995.
(23) Kolodiazhnyi, O. I. Phosphorus Ylides: Chemistry and Applica-
tions in Organic Synthesis; Wiley-VCH: Weinheim, Germany, 1999.
(24) Schmidbaur, H. Angew. Chem., Int. Ed. Engl. 1983, 22, 907.
Navarro, R.; Urriolabeitia, E. P. J . Chem. Soc., Dalton Trans. 1999,
4111.
(25) Schmidbaur, H.; Grohmann, A.; Olmos, M. E. In Gold Progress
In Chemistry, Biochemistry and Technology; Schmidbaur, H., Ed.,
Wiley: Chichester, England, 1999; p 647.
(26) Romeo, I.; Bardaji, M.; Gimeno, M. C.; Laguna, M. Polyhedron
2000, 19, 1837.
(27) Vicente, J .; Chicote, M. T. Coord. Chem. Rev. 1999, 193-195,
1143.
(28) Schmidbaur, H.; Grohmann, A.; Olmos, M. E.; Schier, A. In The
Chemistry of Functional Groups. The Chemistry of Organic Derivatives
of Gold and Silver; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester,
England, 1999; p 227. Barranco, E. M.; Gimeno, M. C.; Laguna, A.
Inorg. Chim. Acta 1999, 291, 60.
(29) Schmidbaur, H.; Zybill, C. E.; Mu¨ller, G.; Kru¨ger, C. Angew.
Chem., Int. Ed. Engl. 1983, 22, 729.
(18) Alejos, P.; Coco, S.; Espinet, P. New J . Chem. 1995, 19, 799.
(19) Vicente, J .; Chicote, M. T.; Abrisqueta, M. D.; J ones, P. G.;
Humphrey, M. G.; Cifuentes, M. P.; Samoc, M.; Luther-Davies, B.
Organometallics 2000, 19, 2968.
(20) Vicente, J .; Chicote, M. T.; Gonza´lez-Herrero, P.; J ones, P. G.;
Humphrey, M. G.; Cifuentes, M. P.; Samoc, M.; Luther-Davies, B.
Inorg. Chem. 1999, 38, 5018. Whittall, I. R.; Humphrey, M. G.;
Houbrechts, S.; Maes, J .; Persoons, A.; Schmid, S.; Hockless, D. C. R.
J . Organomet. Chem. 1997, 544, 277. Whittall, I. R.; Humphrey, M.
G.; Samoc, M.; Luther-Davies, B. Angew. Chem., Int. Ed. Engl. 1997,
36, 370. Naulty, R. H.; Cifuentes, M. P.; Humphrey, M. G.; Houbrechts,
S.; Boutton, C.; Persoons, A.; Heath, G. A.; Hockless, D. C. R.;
Lutherdavies, B.; Samoc, M. J . Chem. Soc., Dalton Trans. 1997, 4167.
Whittall, I. R.; Humphrey, M. G.; Houbrechts, S.; Persoons, A.;
Hockless, D. C. R. Organometallics 1996, 15, 5738.
(21) Tzeng, B. C.; Lo, W. C.; Che, C. M.; Peng, S. M. Chem. Commun.
1996, 181. Muller, 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. Che, C. M.; Yip, H. K.; Lo, W. C.; Peng, S. M. Polyhedron 1994,
13, 887. Hong, X.; Cheung, K. K.; Guo, C. X.; Che, C. M. J . Chem.
Soc., Dalton Trans. 1994, 1867. Li, D.; Hong, X.; Che, C. M.; Lo, W.
C.; Peng, S. M. J . Chem. Soc., Dalton Trans. 1993, 2929. Xiao, H.;
Weng, Y. X.; Peng, S. M.; Che, C. M. J . Chem. Soc., Dalton Trans.
1996, 3155. Xiao, H.; Cheung, K. K.; Che, C. M. J . Chem. Soc., Dalton
Trans. 1996, 3699. Yam, V. W. W.; Choi, S. W. K. J . Chem. Soc., Dalton
Trans. 1996, 4227. Hunks, W. J .; Macdonald, M. A.; J ennings, M. C.;
Puddephatt, R. J . Organometallics 2000, 19, 5063.
(30) Vicente, J .; Chicote, M. T.; Cayuelas, J . A.; Ferna´ndez-Baeza,
J .; J ones, P. G.; Sheldrick, G. M.; Espinet, P. J . Chem. Soc., Dalton
Trans. 1985, 1163.
(31) Vicente, J .; Chicote, M. T.; Saura-Llamas, I.; Turp´ın, J .;
Ferna´ndez-Baeza, J . J . Organomet. Chem. 1987, 333, 129.
(32) (a) Vicente, J .; Chicote, M. T.; Lagunas, M. C.; J ones, P. G. J .
Chem. Soc., Chem. Commun. 1991, 1730. (b) Vicente, J .; Chicote, M.
T.; Lagunas, M. C. Inorg. Chem. 1993, 32, 3748. (c) Vicente, J .; Chicote,
M. T.; Saura-Llamas, I.; J ones, P. G.; Meyer-Ba¨se, K.; Erdbru¨gger, C.
F. Organometallics 1988, 7, 997. (d) Vicente, J .; Chicote, M. T.; Saura-
Llamas, I. J . Chem. Soc., Dalton Trans. 1990, 1941. (e) Vicente, J .;
Chicote, M. T.; Lagunas, M. C.; J ones, P. G.; Ahrens, B. Inorg. Chem.
1997, 36, 4938. (f) Vicente, J .; Chicote, M. T.; Lagunas, M. C. Helv.
Chim. Acta 1999, 82, 1202.
(33) Vicente, J .; Chicote, M. T.; Lagunas, M. C.; J ones, P. G. J . Chem.
Soc., Dalton Trans. 1991, 2579.
(34) Schmidbaur, H.; Gasser, O. Angew. Chem., Int. Ed. Engl. 1976,
15, 502.
(35) Schmidbaur, H.; Sherbaum, F.; Huber, B.; Mu¨ller, G. Angew.
Chem., Int. Ed. Engl. 1988, 27, 419.
(36) Kaska, W. C.; Mitchell, D. K.; Reichelderfer, R. F.; Korte, W.
D. J . Am. Chem. Soc. 1974, 96, 2847.
(37) Petz, W.; Weller, F. Z. Naturforsch., B 1996, 51, 1598.
(38) Goldberg, S. Z.; Raymond, K. N. Inorg. Chem. 1973, 12, 2923.
(22) Kolodiazhnyi, O. I. Tetrahedron 1996, 52, 1855.

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5889
Cp, Cp*),29,41 and [O3Re{C(PPh3)2}][ReO4].42 However,
only the crystal structures of [Ni(CO)n{C(PPh3)2}] (n )
3, 2),40 [CuX{C(PPh3)2}] (X ) Cl, Cp*),29,41 and [O3Re-
{C(PPh3)2}][ReO4]42 have been solved. Here we report
the synthesis of eight new gold(I) complexes with the
ligand C(PPh3)2 and the crystal structure of two of them.
Only a few [Au(CtCR)(ylide)] complexes have been
prepared, by reacting [Au(ylide)(tht)]ClO4 (tht ) tet-
rahydrothiophene) with KCtCR.43 Here we report two
new synthetic methods for such complexes. One of them
uses [Au(acac){C(PPh3)2}] (4), following the method we
have widely used to prepare gold(I) complexes by
reacting [Au(acac)(PR3)] or [Au(acac)2]- with acids.27 We
report the first complexes with the ylide 4-MeC6H4S(O)2-
CHPPh3 and the ylide cation [HC(PPh3)2]+. Kaska et
al. reported unsuccessful attempts to prepare [(OC)5W-
{HC(PPh3)2}]+.39 M. Laguna has recently reported
complexes related to 2, [Au(X){CH(PPh2Me)2}]+ (X )
Cl, C6F5).26
(6.96 g, 2.65 mmol), and 25 g of triphenyl phosphate was
heated at 125-130 °C for 36 h. A highly viscous solution was
obtained. Toluene (30 mL) was added to the cooled reaction
mixture, whereupon a white solid precipitated. It was filtered
by suction and recrystallized from a CH2Cl2-hexane mixture
to give the title compound. Yield: 6.9 g, 46.4%. Mp: 236-238
°C. Anal. Calcd for C26H24IO2PS: C, 55.92; H, 4.33; S, 5.74.
Found: C, 55.82; H, 4.40; S. 5.47. 1H NMR (CDCl3): δ 2.40 (s,
3 H, Me), 6.18 (d, 2 H, CH2, 2J (HP) ) 13 Hz), 7.35 (d, 2 H,
3
C6H4, J (HH) ) 8 Hz), 7.64-7.70 (m, 6 H, Ph or C6H4), 7.77-
7.83 (m, 2 H, Ph or C6H4), 7.93-8.01 (m, 9 H, Ph or C6H4).
31P{1H} (121 MHz, CDCl3): δ 17.6 (s).
Syn th esis of 4-MeC6H4S(O)2CHP P h 3. To a suspension of
[4-MeC6H4S(O)2CH2PPh3]I (1.04 g, 1.86 mmol) in THF (30 mL)
was added an nBuLi solution in hexane (1.6 M, 1.20 mL, 1.92
mmol), and the reactants were stirred at room temperature
for 6 h. The resulting pale yellow solution was evaporated to
dryness, and the resulting solid was thoroughly washed with
water (3 × 5 mL) and recrystallized from a CH2Cl2-hexane
mixture to give the ylide as an off-white solid. Yield: 0.65 g,
81%. Mp: 184 °C. Anal. Calcd for C26H23O2PS: C, 72.54; H,
5.38; S, 7.44. Found, C, 72.05; H, 5.40; S, 6.96. 1H NMR
(CDCl3): 2.31 (s, 3 H, Me), 2.96 (br, 1 H, HCPPh3), 6.99, 7.32
Exp er im en ta l Section
Infrared spectra were recorded in the range 4000-200 cm-1
on a Perkin-Elmer 16F PC FT-IR spectrophotometer with
Nujol mulls between polyethylene sheets. Melting points were
determined on a Reichert apparatus and are uncorrected. C,
H, N, and S analyses were carried out with a Carlo Erba
1106 microanalyzer. Unless otherwise stated, 1H, 13C{1H}, and
31P{1H} NMR spectra were recorded on a Varian Unity 300
spectrometer. Chemical shifts are referenced to the internal
chloroform peak (1H and 13C) and to external H3PO4 (31P). Most
of the carbon resonances have not been assigned, but signals
corresponding to quaternary or ternary carbons are indi-
cated as C or CH with the help of DEPT experiments. [CH2-
(PPh3)2]Br2, [HC(PPh3)2]Br, C(PPh3)2,44 4-MeC6H4S(O)2CH2I,45
4-NCC6H4CtCH, 4-MeOC6H4CtCH, 4-O2NC6H4CtCH,46a
PhCtCC6H4CtCH,46b and PPN[Au(acac)2]47 were prepared by
following either published methods or extensions of them.
Thus, in the preparation of C(PPh3)2 from [HC(PPh3)2]Br and
NaH in diglyme, the reaction mixture was heated at 90-100
°C until the H2 evolution ceased (usually for 1-1.5 h), because
decomposition occurs if refluxed as reported.44 In the purifica-
tion of alkynes or their silyl derivatives by column chroma-
tography, a solvent mixture of Et2O and hexane (1:4) was used
instead of the reported benzene-hexane mixture.46a [CH2-
(PPh3)2](TfO)2 and [4-MeC6H4S(O)2CH2PPh3]TfO (TfO ) CF3-
SO3) were prepared by the metathesis reactions of [CH2(PPh3)2]-
Br2 and [4-MeC6H4S(O)2CH2PPh3]I with thallium(I) triflate,
respectively. Crystals of [4-MeC6H4S(O)2CH2PPh3]TfO (Anal.
Calcd for C27H24F3O5PS: C, 55.85; H, 4.16; S, 11.05. Found:
C, 56.02; H, 4.31; S, 10.92) suitable for the X-ray study were
obtained by slow evaporation of a d6-acetone solution. All
complexes are stable at room temperature in the air, except
complex 4. Complex 3 is not stable in solution (see Discussion).
Syn th esis of [4-MeC6H4S(O)2CH2P P h 3]I. A mixture of
4-MeC6H4S(O)2CH2I (7.83 g, 2.64 mmol), triphenylphosphine
3
(AB system, J (HH) ) 8 Hz, 4 H, C6H4), 7.38-7.70 (m, 15 H,
Ph). 31P{1H} NMR (121 MHz, CDCl3): δ 14.8 (s).
Syn th esis of [Au Cl{C(P P h 3)2}] (1a ). To a suspension of
[AuCl(tht)] (0.68 g, 2.1 mmol) in THF (40 mL) was added a
THF solution (40 mL) of C(PPh3)2 (1.18 g, 2.2 mmol) dropwise
over a period of 20 min under a nitrogen atmosphere. The
reactants were further stirred for 3 h, during which time a
white solid precipitated. It was filtered, washed with Et2O
(2 × 5 mL), and air-dried to give 1a as a white crystalline
solid. Yield: 1.31 g, 80%. The concentration of the filtrate to
ca. 1 mL and addition of Et2O (20 mL) afforded 0.2 g more
of 1a , taking the total yield up to 92%. Dec pt: 250 °C;
lit.29 250 °C for a THF monoadduct. Anal. Calcd for C37H30
-
AuClP2: C, 57.78; H, 3.93. Found: C, 57.51; H, 4.33. IR (cm-1):
ν(Au-Cl), 326 (s). 1H NMR (CDCl3): δ 7.18-7.22, 7.33-7.54,
7.63-7.72, 7.96-8.06 (m, 30 H, Ph). 13C{1H} (75 MHz,
CDCl3): δ -1.46 (t, 1J (CP) ) 102 Hz, C(PPh3)2), 128.23 (m,
1
o-C), 131.14 (s, p-C), 133.20 (apparent triplet, AA′X, | J (CP)
3
+ J (CP)| ) 114 Hz, ipso-C), 133.28 (m, m-C). 31P{1H} NMR
(121 MHz, CDCl3): δ 14.4 (s).
Syn th esis of [Au Cl{CH(P P h 3){S(O)2C6H4Me-4}}] (1b).
To a CH2Cl2 (15 mL) solution of AuCl(tht) (0.23 g, 0.7 mmol)
was added a CH2Cl2 (5 mL) solution of the ylide 4-MeC6H4-
SO2CHPPh3 (0.31 g, 0.71 mmol). The reactants were stirred
for 2 h. The solvent was evaporated in vacuo, and the white
residue so obtained was washed with Et2O (3 × 2 mL).
Recrystallization of the residue from a CH2Cl2-Et2O mixture
afforded 1b as a white crystalline solid. Yield: 0.42 g, 89%.
Mp: 218-220 °C dec. Anal. Calcd for C26H23AuClO2PS: C,
47.10; H, 3.49; S, 4.83. Found: C, 46.69, H, 3.60; S, 4.56. IR
1
(cm-1): ν(Au-Cl), 328 (s). H NMR: δ 2.38 (s, 3 H, Me), 4.93
(d, 2J (PH) ) 10 Hz, 1 H, CHPPh3), 7.21, 7.81 (AB system,
3J (HH) ) 9 Hz, 4 H, C6H4), 7.54-7.60 (m, 6 H, Ph), 7.68-7.74
(m, 3 H, Ph), 7.92-7.99 (m, 6 H, Ph). 13C{1H} NMR (75 MHz,
CDCl3): δ 21.79 (Me), 50.28 (d, 1J (CP) ) 34 Hz, C-PPh3),
(39) Kaska, W. C.; Mitchell, D. K.; Reichelderfer, R. F. J . Organomet.
Chem. 1973, 47, 391.
(40) Petz, W.; Weller, F.; Uddin, J .; Frenking, G. Organometallics
1999, 18, 619.
(41) Zybill, C.; Mu¨ller, G. Organometallics 1987, 6, 2489.
(42) Sundermeyer, J .; Weber, K.; Peters, K.; von Schnering, H. G.
Organometallics 1992, 13, 2560.
1
122.98 (d, J (CP) ) 88 Hz, ipso-C), 127.57 (CH), 129.49 (CH),
129.7 (CH), 134.08 (br, CH), 134.38 (CH), 134.51 (CH) 143.25
(br, C), 144.24 (C). 31P{1H} (121 MHz, CDCl3): δ 20.7 (s). Single
crystals of 1b‚0.5CH2Cl2 were obtained by slow diffusion of
hexane into a CH2Cl2 solution of 1b.
(43) Aguirre, C. J .; Gimeno, M. C.; Laguna, A.; Laguna, M.; Lo´pez
de Luzuriaga, J . M.; Puente, F. Inorg. Chim. Acta 1993, 208, 31.
(44) Driscoll, J . S.; Grisley, D. W., J r.; Pustinger, J . V.; Harris, J .
E.; Matthews, C. N. J . Org. Chem. 1964, 24, 2427.
(45) Cotter, J . L.; Andrews, L. J .; Keefer, R. M. J . Am. Chem. Soc.
1962, 84, 4692.
(46) (a) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara,
N. Synthesis 1980, 627. (b) Lavastre, O.; Cabioch, S.; Dixneuf, P. H.;
Vohlidal, J . Tetrahedron 1997, 53, 7595.
Syn th esis of [Au {HC(P P h 3)2}Cl]TfO (2). A CH2Cl2 solu-
tion (5 mL) of [HC(PPh3)2]TfO (0.33 g, 0.48 mmol) was added
to a CH2Cl2 (15 mL) solution of [AuCl(tht)] (0.15 g, 0.47 mmol).
The reactants were stirred for 2 h. The solvent volume was
concentrated to ca. 2 mL under reduced pressure, and Et2O
(15 mL) was added to precipitate a white solid. It was filtered
by suction, air-dried, and recrystallized from CH2Cl2/Et2O to
give 2 as a white crystalline solid. Yield: 0.39 g, 90%. Mp:
(47) Vicente, J .; Chicote, M. T. Inorg. Synth. 1998, 32, 172.

5890 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
190 °C dec. ΛM ) 159 Ω-1 cm2 mol-1. Anal. Calcd for C38H31
-
Syn th esis of [HC(P P h 3)2][Au (CtCC6H4OMe-4)Cl] (5c).
AuClF3O3P2S: C, 49.66; H, 3.40; S, 3.49. Found: C, 49.63; H,
3.38; S, 3.36. IR (cm-1): ν(Au-Cl), 338 (s). 1H NMR: δ 5.58
(t, 2J (PH) ) 17 Hz, 1 H, HC(PPh3)2), 7.34-7.59, 7.62-7.89 (m,
Yield: 66%. Dec pt: 138-140 °C. ΛM ) 126 Ω-1 cm2 mol-1
.
Anal. Calcd for C46H38AuClOP2: C, 61.31; H, 4.25. Found: C,
60.78; H, 4.43. IR (cm-1): ν(Au-Cl), 332 (s); ν(CtC), 2118 (w).
1
2
30 H, Ph). 13C{1H} (50 MHz, CD2Cl2): δ 7.17 (t, J (CP) ) 45
1H NMR: δ 1.93 (t, J (HP) ) 5 Hz), 3.74 (s, 3 H, OMe), 6.67,
1
3
Hz, HC(PPh3)2), 121.69 (m, AA′X, | J (CP) + J (CP)| ) 92 Hz,
ipso-C), 129.69 (m, o-C), 133.29 (m, m-C), 134.13 (s, p-C).
31P{1H} NMR (121 MHz, CDCl3): δ 22.1 (s).
7.29 (AB system, 3J (HH) ) 9 Hz, 4 H, C6H4), 7.41-7.51 (m,
24 H, Ph), 7.56-7.62 (m, 6 H, Ph). 13C{1H} NMR (75 MHz,
1
CD2Cl2): δ -1.93 (t, J (CP) ) 124 Hz, HC{PPh3}2), 55.09 (s,
Me), 96.98 (CAu), 108.84 (C), 113.31 (CH), 120.05 (C), 126.37
Syn th esis of [(Au Cl)2{µ-C{P P h 3}2}] (3). To a THF solu-
tion (5 mL) of C(PPh3)2 (0.17 g, 0.31 mmol) was added
AuCl(tht) (0.20 g, 0.62 mmol). A white solid started precip-
itating as soon as the two reactants were mixed. After 1 h
of stirring it was filtered off, washed with Et2O (2 × 5 mL),
and air-dried to give 3 as a white solid. Yield: 0.22 g, 70%.
Dec pt: 168-172 °C. Anal. Calcd for C37H30Au2Cl2P2: C, 44.37;
H, 3.02. Found: C, 44.58; H, 3.18. IR (cm-1): ν(Au-Cl), 330
(s). 1H NMR: δ 7.20-7.24, 7.41-7.46, 7.98-8.05 (m, Ph). 31P-
{1H} NMR (121 MHz, CDCl3): δ 21.2 (s). Single crystals
of 3 were obtained by slow diffusion of Et2O into a CH2Cl2
solution.
1
(m, AA′X, | J (CP) + 3J (CP)| ) 102 Hz, ipso-C), 129.39 (appar-
3
ent triplet, AA′X, | J (CP) + 5J (CP)| ) 12 Hz, o-C), 132.84
4
(apparent triplet, AA′X, | J (CP) + 6J (CP)| ) 10 Hz, m-C),
132.91 (CH) 133.20 (CH) 157.51 (C). 31P{1H} NMR (121 MHz,
CDCl3): δ 21.1 (s). Single crystals of 5c suitable for an X-ray
diffraction study were obtained by slow diffusion of hexane
into a CH2Cl2 solution.
Syn th esis of [HC(P P h 3)2][Au (CtCC6H4NO2-4)Cl] (5d ).
Yield: 83%. Dec pt: 146-148 °C. ΛM ) 119 Ω-1 cm2 mol-1
.
Anal. Calcd for C45H35AuClNO2P2: C, 59.00,. H, 3.85, N, 1.53.
Found: C, 58.54; H, 3.82, N, 1.74. IR (cm-1): ν(Au-Cl), 336
(s); ν(CtC), 2116 (w); νasym(NO2), 1504 (s); νsym (NO2), 1336
Syn th esis of [Au (a ca c){C(P P h 3)2}] (4). Solid Tl(acac) (0.2
g, 0.66 mmol) was added to a degassed CH2Cl2 (20 mL) solution
of 1a (0.46 g, 0.6 mmol) under a nitrogen atmosphere. After it
was stirred for 40 min, the resulting suspension was filtered
through Celite, the filtrate was concentrated to ca. 1 mL under
reduced pressure, and Et2O (20 mL) was added to precipitate
a solid, which was filtered and dried under nitrogen to give
complex 4 as a pale yellow solid. Yield: 0.47 g, 94%. Dec pt:
101-102 °C. IR (cm-1): ν(CdO), 1632 (s), 1646 (s). Anal. Calcd
for C42H37AuO2P2: C, 60.58; H, 4.48. Found: C, 60.62; H, 4.56.
1H NMR: δ 1.77 (s, 6 H, Me), 4.1 (s, 1 H, CH), 7.23 (br, 9 H,
Ph), 7.35-7.39 (m, 9 H, Ph), 7.57-7.64 (m, 12 H, Ph).
13C{1H} NMR (50 MHz, CDCl3): δ 7.59 (t, 1J (CP) ) 94 Hz,
1
2
(s). H NMR: δ 1.86 (t, J (HP) ) 5 Hz), 7.38-7.48 (m, Ph or
C6H4NO2), 7.56-7.62 (m, Ph or C6H4NO2), 7.96 (d, Ph or
C6H4NO2). 13C{1H} NMR (75 MHz, CDCl3): δ -1.86 (t, 1J (CP)
) 124 Hz, HC{PPh3}2), 97.70 (C-Au), 121.53 (C), 123.06 (CH)
1
126.18 (m, AA′X, | J (CP) + 3J (CP)| ) 102 Hz, ipso-C), 129.49
3
(apparent triplet, AA′X, | J (CP) + 5J (CP)| ) 12 Hz, o-C), 132.40
4
6
(CH) 132.73 (apparent triplet, AA′X, | J (CP) + J (CP)| ) 10
Hz, m-C), 133.29 (CH) 135.14 (C), 144.65 (C). 31P{1H} NMR
(121 MHz, CDCl3): δ 21.1 (s).
Syn th esis of [Au (CtCP h ){C(P P h 3)2}] (6a ). To a freshly
distilled and degassed chloroform (5 mL) solution of 4 (0.10 g,
0.12 mmol) was added phenylacetylene (0.372 g, 3.64 mmol)
under a nitrogen atmosphere. The reactants were stirred for
1.5 h, after which the volume of the solution was reduced to 1
mL under reduced pressure and Et2O (10 mL) was added to
precipitate a solid which was filtered, washed with Et2O (2 ×
2 mL), and air-dried to afford 6a as a cream-colored solid.
Yield: 90 mg, 90%. Dec pt: 252-254 °C. Anal. Calcd for
3
C(PPh3)2), 29.71(s, Me), 128.25 (apparent triplet, AA′X, | J (CP)
+ 5J (CP)| ) 12 Hz, o-C), 131.10 (CH), 133.02 (apparent triplet,
4
AA′X, | J (CP) + 6J (CP)| ) 10 Hz, m-C), 132.72 (m, AA′X,
1
| J (CP) + 3J (CP)| ) 95 Hz, ipso-C), 201.78 (s, CO). 31P{1H}
NMR (121 MHz, CDCl3): δ 14.3 (s).
Syn th esis of th e Com p lexes [HC(P P h 3)2][Au (CtCR)-
Cl] (5). Complexes 5 were obtained by reacting 1a (0.09-0.13
mmol) with a slight excess of the corresponding alkyne (molar
ratio ca. 1:1.2) in CH2Cl2. The reactants were stirred at room
temperature for 10 h. The solvent was removed under reduced
pressure, and the residue thus obtained was recrystallized
from CH2Cl2 and Et2O.
C
45H35AuP2: C, 64.75; H, 4.22. Found: C, 64.81; H, 4.32. IR
1
(cm-1): ν(CtC), 2104 (w). H NMR: δ 7.03-7.13, 7.19-7.25,
7.32-7.37, 7.44-7.48, 7.65-7.72 (m, 35 H, Ph). 13C{1H} NMR
(75 MHz, CDCl3): δ 9.62 (t, 1J (CP) ) 94 Hz, C(PPh3)2), 101.57
(C), 102.65 (C), 125.11 (C), 127.51 (CH), 128.15 (apparent
3
triplet, AA′X, | J (CP) + 5J (CP)| ) 11.5 Hz, o-C), 130.90 (CH),
4
132.27 (CH), 133.43 (apparent triplet, AA′X, | J (CP) + 6J (CP)|
[HC(P P h 3)2][Au (CtCP h )Cl] (5a ). Yield: 78%. Dec pt:
1
3
145-148 °C. ΛM ) 136 Ω-1 cm2 mol-1. Anal. Calcd for C45H36
-
) 9 Hz, m-C), 133.13 (m, AA′X system, | J (CP) + J (CP)| )
94 Hz, ipso-C). 31P{1H} NMR (121 MHz, CDCl3): δ 16.06 (s).
Syn th esis of [Au (CtCC6H4CN-4){C(P P h 3)2}] (6b). The
off-white complex 6b was prepared as for 6a from 4 (0.17 g,
0.2 mmol) and 4-NCC6H4CtCH (0.7 g, 5.5 mmol) after 3 h of
stirring. Yield: 0.125 g, 71%. Mp: 198-200 °C. Anal. Calcd
for C46H34AuNP2: C, 64.26; H, 3.98; N, 1.62. Found: C, 63.62;
H, 4.00; N, 1.60. IR (cm-1): ν(CtC), 2106 (w); ν(CtN), 2218
(s). 1H NMR: δ 7.1 (m, Ph or C6H4CN), 7.12 (m, Ph or
C6H4CN), 7.15 (m, Ph or C6H4CN), 7.23 (m, Ph or C6H4CN),
7.53-7.60 (m, Ph or C6H4CN). 13C{1H} NMR (75 MHz,
CDCl3): δ 10.68 (t, 1J (CP) ) 95 Hz, C(PPh3)2), 100.19 (C),
AuClP2: C, 62.04; H, 4.17. Found: C, 61.98; H, 4.20. IR (cm-1):
ν(Au-Cl), 332 (s); ν(CtC), 2118 (w). 1H NMR: δ 1.91 (t,
2J (HP) ) 5 Hz), 7.07-7.10, 7.33-7.34, 7.42-7.50, 7.56-7.62
(m, Ph). 13C{1H} NMR (75 MHz, CDCl3): δ -1.89 (t, 1J (CP) )
124 Hz, HC(PPh3)2), 98.28 (C), 110.14 (C), 125.08 (CH), 126.20
1
(m, AA′X system, | J (CP) + 3J (CP)| ) 102 Hz, ipso-C), 127.45
3
5
(CH), 129.49 (apparent triplet, AA′X, | J (CP) + J (CP)| ) 12
4
Hz, o-C), 132.22 (CH), 132.76 (apparent triplet, AA′X, | J (CP)
+ 6J (CP)| ) 10 Hz, m-C), 133.25 (CH). 31P{1H} NMR (121 MHz,
CDCl3): δ 21.1 (s). Single crystals of 5a suitable for an X-ray
diffraction study were obtained by slow diffusion of Et2O into
a CH2Cl2 solution.
3
107.63 (C), 119.32 (C), 128.00 (apparent triplet, AA′X, | J (CP)
5
+ J (CP)| ) 11.5 Hz, o-C), 130.90 (CH), 131.36 (CH), 132.07
[HC(P P h 3)2][Au (CtCC6H4CN-4)Cl] (5b). Yield: 72%. Dec
4
(CH), 133.06 (apparent triplet, AA′X, | J (CP) + 6J (CP)| ) 9
pt: 130-132 °C. ΛM ) 121 Ω-1 cm2 mol-1. Anal. Calcd for
1
Hz, m-C), 132.72 (m, AA′X system, | J (CP) + 3J (CP)| ) 95 Hz,
C
46H35AuClNP2: C, 61.65; H, 3.94; N, 1.56. Found: C, 61.85;
ipso-C). 31P{1H} NMR (121 MHz, CDCl3): δ 16.5 (s).
H, 4.16; N, 1.63. IR (cm-1): ν(Au-Cl), 328 (s); ν(CtN), 2222
(s); ν(CtC), 2112 (w). 1H NMR: δ 1.87 (t, 2J (HP) ) 5 Hz), 7.35
(s), 7.43-7.49, 7.57-7.63 (m, Ph or CNC6H4). 13C{1H} NMR
Syn th esis of [Au (CtCC6H4OMe-4){C(P P h 3)2}] (6c). The
pale yellow complex 6c was prepared as for 6a from 4 (64 mg,
0.077 mmol) and 4-MeOC6H4CtCH (0.308 g, 2.3 mmol) after
stirring the reaction mixture for 4 h. Yield: 55 mg, 82%. Dec
1
(75 MHz, CDCl3): δ -1.58 (t, J (CP) ) 124 Hz, HC{PPh3}2),
97.63 (C), 107.87 (C), 119.38 (CN), 119.70 (C), 126.39 (m, AA′X,
1
| J (CP) + 3J (CP)| ) 102 Hz, ipso-C), 129.66 (apparent triplet,
pt: 140-142 °C. Anal. Calcd for 6c‚0.5CH2Cl2, C46.5H38-
AA′X, | J (CP) + 5J (CP)| ) 12 Hz, o-C), 131.45 (CH), 132.91
AuClOP2: C, 61.56; H, 4.22. Found: C, 61.13; H, 4.25. IR
3
(apparent triplet, AA′X, | J (CP) + 6J (CP)| ) 10 Hz, m-C),
(cm-1): ν(CtC), 2106 (w). 1H NMR: δ 3.74 (s, 3 H, OMe), 5.29
4
133.46 (CH). 31P{1H} NMR (121 MHz, CDCl3): δ 21.1 (s).
(s, 1 H, 0.5 CH2Cl2), 6.66, 7.14 (AB system, J (HH) ) 9 Hz, 4
3

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5891
H, C6H4), 7.24-7.29 (m, 12 H, Ph), 7.38-7.42 (m, 6 H, Ph).
7.67-7.74 (m, 12 H, Ph). 13C{1H} NMR (75 MHz, CD2Cl2): δ
for 7a using 1b (0.2 g, 0.30 mmol), 4-NCC6H4CtCH (42 mg,
0.33 mmol), and Et3N (34 mg, 0.33 mmol). Yield: 0.16 g, 68%.
Dec pt: 162-163 °C. ΛM ) 3 Ω-1 cm2 mol-1. Anal. Calcd for
7b‚0.15CH2Cl2, C35.15H27.3Cl0.3AuNO2PS: C, 55.09; H, 3.59; N,
1.83; S, 4.18. Found: C, 55.18; H, 3.66; N, 1.93; S, 3.86. IR
1
10.86 (t, J (CP) ) 95 Hz C(PPh3)2), 55.47 (s, Me), 100.52 (C),
113.73 (CH), 120.47 (C), 126.75 (C), 128.48 (apparent triplet,
3
AA′X, | J (CP) + 5J (CP)| ) 11 Hz, o-C), 131.34 (CH), 133.04
1
1
(CH), 133.40 (m, AA′X system, | J (CP) + 3J (CP)| ) 95 Hz, ipso-
(cm-1): ν(CtC), 2116 (w); ν(CtN), 2222 (s). H NMR: δ 2.38
4
C). 133.51 (CH), 133.43 (apparent triplet, AA′X, | J (CP) +
(s, 3 H, Me), 4.6 (d, 2J (PH) ) 11 Hz, 1 H, CHP), 5.29 (s, 0.3 H,
6J (CP)| ) 9 Hz, m-C), 157.81 (C). 31P{1H} NMR (121 MHz,
CH2Cl2), 7.2, 7.7 (AB system, J (HH) ) 8 Hz, 4 H, C6H4SO2),
3
CDCl3): δ 15.9(s).
7.34-7.50 (m, 4 H, C6H4CtC), 7.52-7.58 (m, 3 H, Ph), 7.66-
7.71 (m, 6 H, Ph), 7.89-7.96 (m, 6 H, Ph). 13C{1H} NMR (75
MHz, CDCl3): δ 21.76 (s, Me), 55.52 (d, 1J (CP) ) 32 Hz,
CPPh3), 101.04 (C), 108.84 (C), 119.41 (CN), 123.33 (d, 1J (CP)
) 89 Hz, ipso-C), 127.34 (CH), 129.52 (d, 12.7 Hz, o-C), 129.67
(CH), 131.63 (CH), 132.69 (CH), 133.90 (d, 3 Hz, p-C), 134.45
(d, 10 Hz, m-C), 143.48 (C-SO2), 143.79 (C-Me). 31P{1H} NMR
(121 MHz, CDCl3): δ 21.6 (s).
Syn th esis of [Au (CtCC6H4NO2-4){C(P P h 3)2}] (6d ). The
orange crystalline complex 6d was prepared as for 6a from 4
(0.164 g, 0.19 mmol) and 4-NO2C6H4CtCH (0.70 g, 4.75 mmol)
after stirring the reaction mixture for 2.5 h. Yield: 0.12 g, 71%.
Dec pt: 164 °C. Anal. Calcd for C45H34AuNO2P2: C, 61.44; H,
3.90, N, 1.59. Found: C, 61.62; H, 4.06; N, 1.97. IR (cm-1):
1
ν(CtC), 2096 (w); νasym(NO2), 1504 (s); νsym(NO2), 1334 (s). H
NMR: δ 7.20-7.21 (m, 12 H, C6H4NO2 or Ph), 7.34-7.41 (m,
8 H, C6H4NO2 or Ph), 7.64-7.71 (m, 12 H, C6H4NO2 or Ph),
7.97 (d, 9 Hz, 2 H, C6H4NO2 or Ph). 13C{1H} NMR (75 MHz,
CDCl3): δ 10.52 (t, 1J (CP) ) 93 Hz, C(PPh3)2), 101.09 (C),
Syn t h esis of [Au (CtCC6H 4OMe-4){CH (P P h 3){S(O)2-
C6H 4Me-4}}] (7c). White crystalline complex 7c was pre-
pared as for 7a using using 1b (0.155 g, 0.23 mmol),
4-MeOC6H4CtCH (32 mg, 0.24 mmol), and Et3N (26 mg, 0.25
mmol). Yield: 0.125 g, 70%. Dec pt: 108-110 °C. ΛM ) 4 Ω-1
cm2 mol-1. Anal. Calcd for C35H30AuO3PS: C, 55.41; H, 3.99;
S, 4.23. Found: C, 54.94; H, 4.00; S, 4.12. IR (cm-1): ν(CtC),
2114 (w). 1H NMR: δ 2.38 (s, 3 H, Me), 3.74 (s, 3 H, OMe),
4.58 (d, J (PH) ) 11 Hz, 1 H, CHP), 6.7 (d, J (HH) ) 9 Hz, 2
H, C6H4CtC), 7.2, 7.8 (AB system, 3J (HH) ) 8 Hz, 4 H, C6H4-
Me), 7.52-7.61 (m, 6 H, Ph or C6H4CtC), 7.62-7.71 (m, 5 H,
Ph or C6H4CtC), 7.91-7.98 (m, 6 H, Ph or C6H4CtC). 31P-
{1H} NMR (121 MHz, CDCl3): δ 21.4 (s).
3
123.22 (CH), 128.24 (apparent triplet, AA′X, | J (CP) + 5J (CP)|
1
) 11.5 Hz, o-C), 131.07 (CH), 132.90 (m, AA′X system, | J (CP)
+
3J (CP)| ) 95 Hz, ipso-C). 132.55 (CH) 133.39 (apparent
4
triplet, AA′X, | J (CP) + 6J (CP)| ) 9 Hz, m-C), 138.04 (C),
135.12 (C), 144.80 (C-NO2). 31P{1H} NMR (121 MHz,
CDCl3): δ 16.6 (s). Single crystals of 6d suitable for an X-ray
diffraction study were obtained by slow diffusion of hexane
into a THF solution of 6d .
2
3
Syn th esis of [Au (CtCC6H4CtCCP h -4){C(P P h 3)2}] (6e).
Pale yellow 6e was prepared as for 6a from 4 (70 mg, 0.084
mmol) and 4-PhCtCC6H4CtCH (0.432 g, 3.62 mmol) after
stirring the reaction mixture for 5 h. Yield: 55 mg, 70%. Mp:
96-98 °C. Anal. Calcd for C53H39AuP2: C, 68.10; H, 4.20.
Found: C, 68.68; H, 4.20. IR (cm-1): ν(CtC), 2100 (w). 1H
NMR: δ 6.92-6.99, 7.20-7.38, 7.40-7.48, 7.51-7.53, 7.63-
7.72 (m, Ph). 13C{1H} NMR (75 MHz, CDCl3): δ 9.78 (t, 1J (CP)
) 96 Hz, C{PPh3}2), 89.73 (C), 90.35 (C), 101.61 (C), 122.00
(C), 123.07 (C), 123.82 (CH), 128.19 (apparent triplet, AA′X,
Syn t h esis of [Au (CtCC6H 4NO2-4){CH (P P h 3){S(O)2-
C6H4Me-4}}] (7d ). Yellow crystalline complex 7d was pre-
pared as for 7a using 1b (0.18 g, 0 27 mmol), 4-O2NC6H4Ct
CH (54.2 mg, 0.37 mmol), and Et3N (38 mg, 0.37 mmol).
Yield: 0.15 g, 71%. Mp: 160 °C. ΛM ) 4 Ω-1 cm2 mol-1. Anal.
Calcd for 7d ‚0.25CH2Cl2, C34.25H27.5AuCl0.5NO4PS: C, 51.76;
H, 3.49; N, 1.76; S, 4.03. Found: C, 51.80; H, 3.47; N, 1.83; S,
3.94. IR (cm-1): ν(CtC), 2116 (w); νasym (NO2), 1510 (s); νsym
-
1
2
(NO2), 1348 (s). H NMR: δ 2.39 (s, 3 H, Me), 4.61 (d, J (PH)
) 11 Hz, 1 H, CHP), 5.29 (s, 0.5 H, CH2Cl2), 7.22, 7.78 (AB
system,3J (HH) ) 8 Hz, 4 H, C6H4SO2), 7.4, 8.03 (AB system,
3J (HH) ) 9 Hz, 4 H, C6H4CtC), 7.54-7.67 (m, 6 H, Ph), 7.69-
7.72 (m, 3 H, Ph), 7.9-8.00 (m, 6 H, Ph), 13C{1H} NMR (75
MHz, CDCl3): δ 21.79 (s, Me), 55.48 (d, 1J (CP) ) 32 Hz, CHP),
101.10 (C), 123.22 (d, 1J (CP) ) 89 Hz, ipso-C), 123.34 (C),
127.30 (CH), 127.56 (CH), 129.54 (d, 2J (CP) ) 13 Hz, o-C),
132.69 (CH), 133.77 (C), 134.43 (d, 3J (CP) ) 10 Hz, m-C),
134.76 (CH), 143.36 (C-SO2), 143.83 (C-Me), 145.37 (C-NO2).
31P{1H} NMR (121 MHz, CDCl3): δ 21.8 (s)
3
| J (CP) + 5J (CP)| ) 12 Hz, o-C), 128.38 (CH), 128.5 (CH),
1
130.97 (CH), 131.60 (CH) 132.0 (m, AA′X system, | J (CP) +
3J (CP)| ) 95 Hz, ipso-C), 132.19 (CH), 133.40 (apparent triplet,
4
AA′X, | J (CP) + 6J (CP)| ) 9 Hz, m-C). 31P{1H} NMR (121 MHz,
CDCl3): δ 16.2 (s).
Syn th esis of [Au (CtCP h ){CH(P P h 3){S(O)2C6H4Me-4}}]
(7a ). A CH2Cl2 (10 mL) solution of 1b (0.112 g, 0.17 mmol)
was added to a stirred CH2Cl2 (5 mL) solution of phenylacety-
lene (0.0186 g, 0.18 mmol) and triethylamine (0.0218 g, 0.21
mmol). The reaction mixture was stirred for 8 h. The volume
of the solution was reduced to ca. 2 mL under reduced
pressure, and Et2O (20 mL) was added to precipitate a white
solid, which was filtered and washed with water (2 × 5 mL)
to remove [NHEt3]Cl. The solid residue was dissolved in
CH2Cl2 (20 mL), the solution was passed through anhydrous
MgSO4, and the solvent was removed under reduced pressure.
The residue was recrystallized from CH2Cl2/hexane to afford
7a as a white crystalline solid (0.098 g, 79.6%). Mp: 160 °C.
ΛM ) 3 Ω-1 cm2 mol-1. Anal. Calcd for C34H28AuO2PS: C,
56.05; H, 3.87; S, 4.40. Found: C, 56.23; H, 4.02; S, 4.12. IR
Syn th esis of [Au (CtCC6H4CtCP h -4){CH(P P h 3){S(O)2-
C6H4Me-4}}] (7e). The yellow complex 7e was prepared as
for 7a from 1b (0.12 g, 0 18 mmol), PhCtCC6H4CtCH (44
mg, 0.21 mmol), and Et3N (22 mg, 0.21 mmol). Yield: 75 mg,
50%. Dec pt: 134-136 °C. ΛM ) 8 Ω-1 cm2 mol-1. Anal. Calcd
for C42H32AuO2PS: C, 60.87; H, 3.89; S, 3.86. Found: C, 61.05;
H, 4.11; S, 3.62. IR (cm-1): ν(CtC), 2108 (w). 1H NMR: δ 2.39
(s, 3 H, Me), 4.60 (d, 2J (PH) ) 11 Hz, 1 H, CHP), 7.23, 7.81
3
(AB system, J (HH) ) 8 Hz, 4 H, C6H4SO2), 7.30-7.34 (m, 6
H, C6H4CtC or Ph), 7.42-7.70 (m, 12 H, C6H4CtC or Ph),
7.91-7.98 (m, 6 H, C6H4CtC or Ph). 13C{1H} NMR (75 MHz,
CDCl3): δ 21.71 (s, Me), 55.04 (d, 1J (CP) ) 32 Hz, CHP), 89.86
1
(cm-1): ν(CtC), 2118 (w). H NMR: δ 2.38 (s, 3 H, Me); 4.60
(d, 2J (PH) ) 11 Hz, 1 H, HCP), 7.33, 7.81 (AB system, 3J (HH)
) 9 Hz, 4 H, C6H4), 7.09-7.23 (m, 4 H, Ph), 7.52-7.59 (m
, 6 H, Ph), 7.66-7.70 (m, 4 H, Ph), 7.91-7.98 (m, 6 H, Ph).
13C{1H} NMR (75 MHz, CDCl3): δ 21.75 (s, Me); 55.34 (d,
1J (CP) ) 32 Hz, HCPPh3), 102.14 (Au-C), 123.45 (d, 89 Hz,
ipso-C), 125.10 (C), 125.95 (CH), 126.31 (C), 127.37 (CH),
127.77 (CH), 128.7 (C), 129.49 (d, 1J (CP) ) 13.0 Hz, o-C),
132.27 (CH), 133.79 (d, 2.3 Hz, p-C), 134.51 (d, 9.7 Hz, m-C),
143.46 (C-SO2), 143.51 (C-Me). 31P{1H} NMR (121 MHz,
CDCl3): δ 21.4 (s).
1
(C), 90.35 (C), 101.45 (C), 120.62 (C), 123.42 (d, J (CP) ) 89
Hz, ipso-C), 125.10 (C), 125.58 (C), 126.73 (C), 127.03 (C),
127.30 (CH), 127.56 (C), 128.56 (CH), 129.67 (d, 2J (CP) ) 12.7
Hz, o-C), 129.79 (CH), 131.44 (CH), 131.79 (CH), 132.11 (CH),
4
3
134.13 (d, J (CP) ) 2.9 Hz, p-C), 134.63 (d, J (CP) ) 10 Hz,
m-C), 143.42 (CSO2), 144.11 (CMe). 31P{1H} NMR (121 MHz,
CDCl3): δ 21.6 (s).
Syn th esis of [Au {HC(P P h 3)2}2](TfO)3 (8a ). Solid [CH2-
(PPh3)2](TfO)2 (0.553 g, 0.660 mmol) was added to a solution
of PPN[Au(acac)2] (0.308 g, 0.330 mmol) in 1.5 mL of CH2Cl2.
The resulting mixture was stirred for 5 h, during the course
Syn t h esis of [Au (CtCC6H 4CN-4){CH (P P h 3){S(O)2-
C6H4Me-4}}] (7b). The off-white complex 7b was prepared as

5892 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
Ta ble 1. Su m m a r y of X-r a y Da ta for [4-MeC6H4S(O)2CH2P P h 3]TfO a n d th e Com p lexes 1b‚0.5CH2Cl2 a n d
3‚3CH2Cl2
[4-MeC6H4S(O)2CH2PPh3]TfO
1b‚0.5CH2Cl2
3‚3CH2Cl2
formula
Mr
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
C
27H24F3O5PS2
C
26.5H24AuCl2O2PS
C40H36Au2Cl8P2
1256.16
monoclinic
P21/n
13.3093(8)
18.7357(12)
17.7001(12)
90
105.100(3)
90
4261.31(5)
4
580.55
triclinic
P1h
705.35
monoclinic
P21/n
10.7675(16)
14.957(2)
16.499(2)
90
96.827(10)
90
2638.3(6)
4
9.3844(10)
11.1949(12)
13.4673(14)
69.404(8)
84.271(8)
83.508(8)
1313.2(2)
2
Z
T (K)
173(2)
1.468
600
0.322
4528
4528/373/377
1.030
173(2)
1.776
1372
5.941
4641
133(2)
1.958
2400
7.484
12 473
12 473/432/469
0.978
Dcalcd (Mg m-3
F(000)
)
µ (mm-1
no. of indep rflns
no. of data/restraints/params
S(F2)
)
4641/266/312
0.899
wR2 (all rflns)
R1 (I > 2σ(I))
0.0899
0.0342
0.303
0.0446
0.0233
0.619
0.0539
0.0225
1.602
max ∆F (e Å-3
)
Ta ble 2. Su m m a r y of X-r a y Da ta for Com p lexes 5a , 5c, 6d ‚THF , a n d 8b
5a
5c
6d ‚THF
8b
formula
Mr
cryst syst
space group
a (Å)
C
45H36AuClP2
C
46H38AuClOP2
C
49H42AuNO3P2
C
53H46AuF3O7P2S3
871.09
monoclinic
Cc
16.7631(12)
15.7320(11)
15.0215(11)
90
111.100(4)
90
3695.8(5)
4
901.12
monoclinic
Cc
17.1531(11)
15.8402(11)
15.1264(8)
90
112.657(3)
90
3792.8(4)
4
951.74
triclinic
P1h
1206.98
monoclinic
P21/n
16.098(3)
15.402(2)
20.668(3)
90
106.222(10)
90
4920.4(13)
4
11.7875(11)
13.4391(12)
14.8753(12)
78.828(3)
68.060(3)
68.627(3)
2030.9(3)
2
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
Z
T (K)
133(2)
1.566
1728
4.171
10 759
10 759/147/443
0.951
133(2)
1.578
1792
4.069
10 986
10 986/152/462
0.982
133(2)
1.556
952
3.745
11 826
11 826/163/ 505
1.013
173(2)
1.629
2416
3.247
8654
Dcalcd (Mg m-3
F(000)
)
µ (mm-1
no. of indep rflns
no. of data/restraints/params
S(F2)
)
8654/551/616
0.853
wR2 (all rflns)
R1 (I > 2σ(I))
0.0401
0.0218
1.604
0.0359
0.0179
0.995
0.0597
0.0249
2.110
0.0517
0.0266
0.596
max ∆F (e Å-3
)
of which a white solid precipitated. The solid was filtered by
suction, washed with cold CH2Cl2 (2 × 1 mL), and air-dried to
give 8a as a white solid. Yield: 70%. Dec pt: 250-252 °C. ΛM
) 254 Ω-1 cm2 mol-1. Anal. Calcd for C75H62AuF9O9P4S3: C,
1000 CCD (ω- and φ-scans, 2θmax ) 60°, absorption correction
using multiple scans). Structures were refined anisotropically
on F2 using the program SHELXL-97 (G. M. Sheldrick,
University of Go¨ttingen). Hydrogen atoms were included using
a riding model or rigid methyl groups. Light atom U values
were restrained to be approximately equal (commands SIMU,
DELU). Disordered groups were refined using appropriate
systems of similarity restraints. Other details of the data
collection and refinement are given in Tables1 and 2.
Sp ecia l F ea tu r es of th e Refin em en t. [4-MeC6H4S(O)2-
CH2PPh3]TfO: the triflate anion is disordered over two posi-
tions with occupations of ca. 89:11. Compound 1b: the solvent
is disordered over two positions with occupations ca. 70:30.
Compounds 5a and 5c: the structures were refined as enan-
tiomorphic twins, with twinning ratios 0.333:0.667 and 0.433:
0.567, respectively. Compound 8b: the triflate is disordered
over two equally occupied sites.
1
53.14; H, 3.69; S, 5.67. Found: C, 52.94; H, 3.57; S, 5.26. H
NMR (d6-acetone): δ 5.69 (t, 2J (HP) ) 16 Hz, 2 H, CH), 7.29-
7.77 (m, 60 H, Ph). 31P{1H} NMR (121 MHz, d6-acetone): δ
26.1 (s).
Syn th esis of [Au {CH(P P h 3){S(O)2C6H4Me-4}}2]TfO (8b).
White complex 8b was prepared as for 8a from PPN[Au(acac)2]
(0.100 g, 0.108 mmol) and [4-MeC6H4S(O)2CH2PPh3]TfO (0.126
g, 0.217 mmol) in 1 mL of THF. Yield: 66%. Dec pt: 188-190
°C. ΛM ) 147 Ω-1 cm2 mol-1. Anal. Calcd for C53H46
-
AuF3O7P2S3: C, 52.74; H, 3.84; S, 7.97. Found: C, 52.40; H,
1
3.93; S, 7.68. H NMR (d6-acetone): δ 2.34 (s, 6 H, Me), 5.32
3
(d, 11 Hz, 2 H, CH), 7.09 (d, J (HP) ) 8 Hz, 4 H, C6H4), 7.43-
7.51 (m, 16 H, Ph or C6H4), 7.75-7.86 (m, 18 H, Ph or C6H4).
31P{1H} NMR (121 MHz, d6-acetone): δ 20.2 (s).
X-r a y Str u ctu r e Deter m in a tion s. Data were collected
using Mo KR radiation (λ ) 0.710 73 Å). For compounds
[4-MeC6H4S(O)2CH2PPh3]TfO, 1b, and 8b a Siemens P4 dif-
fractometer was used (ω-scans, 2θmax ) 50°, absorption cor-
rection by ψ-scans); for the other structures, a Bruker SMART
Resu lts a n d Discu ssion
Syn t h esis of [4-MeC6H 4SO2CH 2P P h 3]X (X ) I,
CF 3SO3). The triflate salt of the phosphonium cation
[4-MeC6H4SO2CH2PPh3]+ has recently been described

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5893
Ch a r t 1
Sch em e 1
by Zhdankin starting from 4-MeC6H4SO2CH2I and
following a three-step synthetic procedure.48 We report
the synthesis of the iodide salt by heating the same
starting material, triphenylphosphine, and triphenyl
phosphate at 125-130 °C for 36 h, extending the
procedure used for the synthesis of the diphosphonium
salt [CH2(PPh3)2]Br2.44 The triflate salt was prepared
by reacting the iodide with thallium(I) triflate and the
ligand of [AuCl(tht)]. In other words, complex 1a
behaves as a ligand. Solutions of complex 3 in chlori-
nated solvents (CH2Cl2 or CHCl3) decompose slowly. We
have reported di-, tri-, and tetranuclear complexes
containing C-bridging ylides which, in contrast to 3, are
all cationic and have been prepared by reacting the
phosphonium or arsonium salts [R3AsCH2C(O)R′]+, [Au-
{HC(PPh3)(CO2R)}2]+, [OC{CH2L′}2]2+, and [Ph2P(CH2-
CO2R)2]ClO4 with [Au(acac)PR′3] or PPN[Au(acac)2].
The resulting complexes are of the following types:
[(AuEPh3)2{µ-C(PPh3)R}]+ (E ) P, As; R ) C(O)Me,
C(O)Ph, C(O)NMe2, CO2Me, CO2Et, CN, pyridyl-2), [Au-
{C(PPh3)(AuPPh3)(CO2R}2]+ (R ) Me, Et), [(AuL)2{µ-
{C(L)C(O)CH(L)(AuL)}}]2+ (L ) PPh3), [(AuL)4{µ-{C-
(L′)}2C(O)}}]2+ (L ) PMe2Ph, L′ ) PPh3), and [(AuL)2{µ-
C(CO2R)PPh2CH(AuL)CO2R)}]+ (L ) PPh3, R ) Me, Et;
L ) PMe2Ph, R ) Me; L ) PPh2(C6H4OMe-4), R )
Et).30-33 Schmidbaur also reported the cationic complex
[(AuPPh3)2{µ-C(PMePh2)2}]2+ by reacting the ylide with
2 equiv of [AuBr(PPh3)].35 The only complex related to
3 is [(AuMe)2{µ-C(PMe3)2}],34 reported as the product
of the reaction of the ylide with 2 equiv of [AuMe(PMe3)];
it starts decomposing slowly if left in chlorinated
solvents (CH2Cl2 or CHCl3). The rest of all the complexes
could be handled in air without any problem.
The reaction of 1a with Tl(acac) using a 1:1.4 molar
ratio gives [Au(acac){C(PPh3)2}] (4), which is the first
(acetylacetonato)gold(I) complex with an ylide ligand
(Scheme 1). As shown below, it can be used to prepare
the complexes [Au(CtCR){C(PPh3)2}] by reaction with
alkynes. Complex 4 decomposes slowly at room temper-
ature if left in the air, but it can be stored indefinitely
at -10 °C under nitrogen.
Rea ctivity of [Au {C(P P h 3)2}Cl] (1a ) tow a r d Al-
k yn es. Syn th esis of th e Com p lexes [HC(P P h 3)2]-
[Au (CtCR)Cl] (5). In an attempt to prepare the
complexes [Au(CtCR){C{PPh3}2}] (R ) Ph, 4-MeOC6H4)
we reacted [Au{C(PPh3)2}Cl] (1a ) with the correspond-
n
ylide by dehydroiodination of the iodide salt by BuLi
in THF. C-Sulfonyl-substituted ylides are among the
most stable ylides, as attributable to the efficient
delocalization of the negative charge on the ylide carbon
over the oxygen atoms (see Chart 1). They have been
obtained by various methods as stable crystalline sub-
stances. We are not aware of the existence of metal
complexes of these ligands.22,23
Syn th esis of th e Com p lexes [Au Cl(ylid e)], [Au Cl-
(ylide)]TfO, [(Au Cl)2{µ-ylide}], an d [Au (acac)(ylide)].
The reaction of AuCl(tht) (tht ) tetrahydrothiophene)
with the ylide C(PPh3)2 in THF or with 4-MeC6H4SO2-
CHPPh3 or [HC(PPh3)2]TfO in CH2Cl2 (1:1 molar ratio)
readily afforded the corresponding complexes [AuCl-
(ylide)]Xn (n ) 0, ylide ) C(PPh3)2 (1a ), 4-MeC6H4SO2-
CHPPh3 (1b), n ) 1, X ) TfO, ylide ) [HC(PPh3)2]+ (2))
in good to excellent yields (Scheme 1). The only previ-
ously known gold complex with the diylide C(PPh3)2 is
1a ,29 preliminarily reported by Schmidbaur and ob-
tained by reacting C(PPh3)2 with [AuCl(CO)]. Complex
2 is the first gold complex with the ylide cation [HC-
(PPh3)2]+.25
When we attempted to prepare 1a in a large quantity
(about 1 g), a white solid precipitated immediately. On
isolation, this showed NMR data different from those
of 1a , and C and H analyses indicated that the complex
could be the dinuclear [(AuCl)2{µ-C(PPh3)2}] (3) (Scheme
1). This was confirmed by reacting [AuCl(tht)] and
C(PPh3)2 in a 2:1 molar ratio. The insolubility of 3 and
a localized excess of AuCl(tht) in the 1:1 reaction could
explain its unexpected formation in the large-scale
synthesis of 1a . These results indicate that the coordi-
nated ylide C(PPh3)2 in 1a retains some basic character
after coordination to AuCl, because it replaces the tht
(48) Zhdankin, V. V.; Erickson, S. A.; Hanson, K. J . J . Am. Chem.
Soc. 1997, 119, 4775.

5894 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
Sch em e 2
the result of reactions of the polymeric complex [Au-
(CtCPh)]n with the corresponding halides. The latter
complexes were prepared by reacting [Au(CtCH)2]-
with the corresponding [AuX2]-. The method used to
prepare complexes 5 represents a third way to synthe-
size these types of complexes.
Syn th esis of th e Com p lexes [Au (CtCR)-
{C(P P h 3)2}] (6). The desired complexes [Au(CtCC6H4R-
4){C{PPh3}2}] (R ) H (6a ), CN (6b), OMe (6c), NO2
(6d ), CtCPh (6e)) were prepared by the reaction of [Au-
(acac){C(PPh3)2}] (4) with a large excess of alkynes (ca.
1:25-30) in freshly distilled and degassed chloroform
(Scheme 2). This is a new example of the “acac” method
of synthesis of gold complexes.27 To establish the exact
course of the reactions, they were first monitored by 31
P
NMR spectroscopy. The main peaks were observed at δ
14.35 ppm for 4, around δ 16 ppm for complexes 6, and
δ 21.1 ppm (weak, coincident with that of [HC(PPh3)2]+).
The 1:1 reaction with PhCtCH was incomplete even
after 40 h. This slowness contrasts with the usually fast
reactions of other acac gold(I) complexes use to proceed
and also with the reactions of 1a with alkynes to give
complexes 5. The reaction rate increased with the molar
ratio of the alkyne to complex 4, but not significantly.
For example, in the reaction with a 3:1 molar ratio, 4
was only 50% consumed after 10 h and was totally
consumed after 30 h. With a 10:1 molar ratio only 33%
was consumed after 3 h and 100% after 24 h. If the
reaction is left for a longer time, then the peak at 21.1
ppm ([HC(PPh3)2]+), always present in the mixture in
minor amounts, grows with respect to that correspond-
ing to 6a . All these data suggest that the first reaction
is [Au(acac){C(PPh3)2}] + PhCtCH f [Au(CtCPh)-
(C{PPh3}2)] (6a ) + Hacac and that the excess of the
alkyne slowly protonates and replaces the ylide ligand
from 6a following the reaction: [Au(CtCPh){C(PPh3)2}]
+ PhCtCH f [HC(PPh3)2][Au(CtCR)2]. Finally, a 30:1
molar ratio reaction allowed a complete conversion of
reactants in 6a in 1.5 h with only minor amounts of the
ing terminal alkynes in the presence of Et3N (1:1:1
molar ratio). However, we isolated instead complexes
of the type [HC(PPh3)2][Au(CtCR)Cl] (5) (Scheme 2).
This result indicates that the deprotonating character
of the coordinated ylide C(PPh3)2 in 1a is better than
that of the free Et3N. This result is in agreement with
the basic or ligand character of 1a when it reacts with
[AuCl(tht)], replacing tht to give the dinuclear complex
3. To ascertain whether the triethylamine was neces-
sary in these reactions, we monitored the reactions of
1a with alkynes in the absence of Et3N by 31P NMR
spectroscopy. It was observed that the reactions took
place and were complete in about 5-6 h. However, a
parallel study in the presence of Et3N showed that these
reactions were much faster than in the absence of the
base, being complete in 0.5 h. Although Et3N acts as a
catalyst in these reactions, we decided to prepare the
complexes [HC(PPh3)2][Au(CtCC6H4R-4)Cl] (R ) H
(5a ), CN (5b), OMe (5c), NO2 (5d )) in the absence of
Et3N to avoid contaminations. The only reported com-
plexes of the type Q[Au(CtCR)X] are those with R )
Ph and X ) Cl, Br, I49 and with R ) H and X ) Cl, Br,
I.50,51 The former were only preliminarily reported as
1
21.1 ppm peak in the H NMR spectrum of the mixture.
In view of these observations, reactions in NMR tubes
were carried out between 4 and variable amounts of
alkynes to optimize the molar ratios and the time
required to prepare complexes 6. Depending on the
alkyne, the reactions were complete within 2-5 h of
mixing when 25-30 equiv of the alkyne was used.
Complex 4 starts decomposing if kept in solution for a
longer time. The large excess of the alkyne could be
easily recovered from the ether washings and can be
purified either by chromatography or recrystallization
for further use.
Syn th esis of Com p lexes [Au (CtCC6H4R-4){CH-
(P P h 3){S(O)2C6H4Me-4}}] (R ) H (7a ), NC (7b), OMe
(7c), NO2 (7d ), CtCP h (7e)). The complex [AuCl{CH-
(PPh3){S(O)2C6H4Me-4}}] (1b) reacts with terminal
alkynes in the presence of Et3N differently from 1a ,
giving complexes 7 (Scheme 2). Complexes 7 are air and
moisture stable and show the expected NMR spectra.
However, CDCl3 solutions of complexes 7a , 7c, and 7e
show small peaks at around 22.3 ((0.01) and 14.82
((0.01) ppm in their 31P NMR spectra, integrated to
approximately 1/8 and 1/10 for 7a , 1/6 and 1/7 for 7c,
and 1/13 and 1/16 with respect to the main peak of
complex 7 at around 21.5 ppm. Such peaks could not
(49) Abu-Salah, O. M.; Al-Ohaly, A. R. Inorg. Chim. Acta 1983, 77,
L159.
(50) Vicente, J .; Chicote, M. T.; Abrisqueta, M. D. J . Chem. Soc.,
Dalton Trans. 1995, 497.
(51) Vicente, J .; Chicote, M. T.; Abrisqueta, M. D.; J ones, P. G.
Organometallics 1997, 16, 5628.

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5895
Sch em e 3
Figu r e 1. Thermalellipsoid plot ofthecation [4-MeC6H4S(O)2-
CH2PPh3}]+ (50% probability level) with the labeling
scheme. Selected bond lengths (Å) and angles (deg): P-C(41)
) 1.7927(18), P-C(21) ) 1.7932(18), P-C(31) ) 1.7935-
(19), P-C(1) ) 1.8145(18), S(1)-O(1) ) 1.4358(14), S(1)-
O(2) ) 1.4385(14), S(1)-C(11) ) 1.7549(19), S(1)-C(1) )
1.7968(18), S(2)-O(5) ) 1.426(2), S(2)-O(3) ) 1.428(3),
S(2)-O(4) ) 1.429(2), S(2)-C(99) ) 1.809(3), C(99)-F(1)
) 1.306(4), C(99)-F(3) ) 1.311(3), C(99)-F(2) ) 1.329(4);
C(41)-P-C(21) ) 107.90(9), C(41)-P-C(31) ) 110.13(8),
C(21)-P-C(31) ) 110.07(9), C(41)-P-C(1) ) 106.37(8),
C(21)-P-C(1) ) 110.95(8), C(31)-P-C(1) ) 111.31(9),
O(1)-S(1)-O(2) ) 119.45(9), O(1)-S(1)-C(11) ) 108.71-
(9), O(2)-S(1)-C(11) ) 107.68(9), O(1)-S(1)-C(1) ) 108.33-
(8), O(2)-S(1)-C(1) ) 105.05(8), C(11)-S(1)-C(1) ) 106.98-
(9), S(1)-C(1)-P ) 116.42(10).
arise from impurities, because they remain with the
same intensity ratio after several recrystallizations.
This led us to believe that, although in the solid these
complexes are pure compounds, in agreement with their
elemental analyses, when dissolved, they decompose to
give other product(s) with which they are in equilibrium.
The peak at 14.82 ppm could be due to free ylide (δ 14.8
ppm), suggesting an equilibrium of complexes 7 with
the ylide and [Au(CtCR)]n. The peak at 22.3 ppm could
be caused by the ionic species [Au{CH(PPh3){S(O)2C6H4-
Me-4}}2][Au(CtCR)2] (the resonance in the complex
[Au{CH(PPh3){S(O)2C6H4Me-4}}2]TfO (8b) appears at
20.2 ppm). The molar conductivities of solutions in
acetone of complexes 7 are in the range 3-8 Ω-1 cm2
mol-1. Because of the different concentrations required
to measure 31P NMR spectra and conductivities, it is
not possible to calculate the molar conductivities refer-
enced to the ionic species.
Syn th esis of th e Ca tion ic Com p lexes [Au {HC-
(P P h 3)2}2](TfO)3 (8a ) a n d [Au {CH (P P h 3){S(O)2-
C6H4Me-4}}2]TfO (8b). The reactions of PPN[Au-
(acac)2] with the phosphonium salts [H2C(PPh3)2](TfO)2
and [4-MeC6H4S(O)2CH2PPh3]TfO in a 1:2 stoichiom-
etry afforded the cationic complexes 8a and 8b, respec-
tively (Scheme 3). These complexes are white crystal-
line solids, and their solutions in acetone-d6 show
singlets at δ 26.1 and 20.4, respectively, indicating that
the two phosphorus atoms are equivalent in the com-
plexes.
Str u ctu r es of th e Com p lexes. The crystal struc-
tures of [4-MeC6H4S(O)2CH2PPh3]TfO (Figures 1 and
2), 1b‚0.5CH2Cl2 (Figures 3-5), 3‚3CH2Cl2 (Figure 6),
5a (Figures 7 and 8), 5c (Figure 9), 6d ‚THF (Figures
10 and 11), and 8b (Figures 12 and 13) have been
F igu r e 2. Packing diagram showing hydrogen bond
interactions in [4-MeC6H4S(O)2CH2PPh3}]TfO.
determined. Tables 1 and 2 give a summary of X-ray
data for these complexes.
The structure of the phosphonium salt [4-MeC6H4S(O)2-
CH2PPh3 ]TfO (Figure 1) reveals the expected distorted-
tetrahedral geometry around the phosphorus and sulfur
atoms. The C-P-C bond angles are similar to those
found in the corresponding ylide complexes 1b and 8b.
The O-S-O bond angle (119.45(9)°) is wider than the
C-S-O and C-S-C bond angles (105.05(8)-108.71-
(9)°), probably due to the multiple-bond character of the

5896 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
F igu r e 3. Thermal ellipsoid plot of the complex 1b‚
0.5CH2Cl2 (50% probability level) with labeling scheme.
Selected bond lengths (Å) and angles (deg): Au-C(1) )
2.067(4), Au-Cl(1) ) 2.2914(10), S-O(1) ) 1.437(3), S-O(2)
) 1.446(3), S-C(11) ) 1.771(4), S-C(1) ) 1.771(4), P-C(1)
) 1.792(4), P-C(21) ) 1.800(4), P-C(41) ) 1.803(4),
F igu r e 5. Packing diagram showing all hydrogen bond
interactions in 1b‚0.5CH2Cl2.
P-C(31)
) 1.804(4); C(1)-Au-Cl(1) ) 178.36(11),
O(1)-S-O(2) ) 118.39(18), O(1)-S-C(11) ) 105.53(18),
O(2)-S-C(11) ) 107.21(18), O(1)-S-C(1) ) 106.91(18),
O(2)-S-C(1) ) 108.96(18), C(11)-S-C(1) ) 109.62(18),
C(1)-P-C(21) ) 111.88(18), C(1)-P-C(41) ) 114.17(18),
C(21)-P-C(41) ) 108.44(18), C(1)-P-C(31) ) 108.23(18),
C(21)-P-C(31) ) 106.02(18), C(41)-P-C(31) ) 107.70-
(18), S-C(1)-P ) 118.2(2).
F igu r e 6. Thermal ellipsoid plot of the complex 3‚3CH2-
Cl2 (30% probability level) with the labeling scheme.
Selected bond lengths (Å) and angles (deg): Au(1)-C(1) )
2.078(3), Au(1)-Cl(1) ) 2.2974(8), Au(1)-Au(2) ) 3.1432-
(2), Au(2)-C(1) ) 2.074(3), Au(2)-Cl(2) ) 2.2946(7), P(2)-
C(1) ) 1.776(3), P(2)-C(61) ) 1.809(3), P(2)-C(51) )
1.819(3), P(2)-C(41) ) 1.825(3), P(1)-C(1) ) 1.776(3),
P(1)-C(31) ) 1.809(3), P(1)-C(11) ) 1.819(3), P(1)-C(21)
) 1.819(3); C(1)-Au(1)-Cl(1) ) 175.29(8), C(1)-Au(2)-
Cl(2) ) 176.96(8), C(1)-P(2)-C(61) ) 113.42(13), C(1)-
P(2)-C(51) ) 111.09(13), C(61)-P(2)-C(51) ) 104.64(13),
C(1)-P(2)-C(41) ) 115.35(13), C(61)-P(2)-C(41) ) 103.55-
(13), C(51)-P(2)-C(41) ) 107.97(13), C(1)-P(1)-C(31) )
111.16(13), C(1)-P(1)-C(11) ) 116.40(13), C(31)-P(1)-
C(11) ) 107.49(13), C(1)-P(1)-C(21) ) 112.20(13), C(31)-
P(1)-C(21) ) 105.25(13), C(11)-P(1)-C(21) ) 103.50(13),
P(1)-C(1)-P(2) ) 117.30(15), P(1)-C(1)-Au(2) ) 108.06-
(13), P(2)-C(1)-Au(2) ) 111.14(13), P(1)-C(1)-Au(1) )
110.20(13), P(2)-C(1)-Au(1) ) 110.07(14).
F igu r e 4. Packing diagram showing Au‚‚‚Au and hydro-
gen bond interactions in the dimeric unit of 1b‚0.5CH2Cl2.
S-O bonds (see Chart 1). The S-O (1.4358(14), 1.4385-
(14) Å) and P-Ph (1.7927-1.7935 Å) bond distances are
not significantly different from those in its metalated
derivatives (1b, S-O ) 1.437(3), 1.446(3) Å, P-Ph )
1.800-1.804(4) Å; 8b, S-O ) 1.440(2)-1.446(3) Å,
3
P-Ph ) 1.792-1.813(4) Å). However, the P-Csp bond
length (1.8145(18) Å) in the phosphonium salt is sig-
nificantly longer than the corresponding distance in 1b
3
(1.792(4) Å). In 8b, one P-Csp (Au) distance is signifi-
cantly shorter (1.798(4) Å) and the other one marginally
shorter (1.805(4) Å) than that in the phosphonium salt.
The crystal structure of the ylide 4-MeC6H4S(O)2-
CHPPh3 has been solved.52 Although it is not too
reliable, the P-CH bond length is considerably shorter
(1.709(19) Å) and one of the S-O values (1.469(14) Å)
longer than the above values. The other S-O distance
(1.444(15) Å) is similar to those found in the phospho-
nium salt or complexes 1b and 8b. Probably, the P-C
bond order in these complexes is intermediate between
the single bond in the phosphonium salt and that in the
free ylide (see Chart 1). A similar conclusion was
1
(52) Speziale, A. J .; Ratz, K. W. J . Am. Chem. Soc. 1965, 87, 5603.
reached when IR and H NMR spectra were compared

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5897
F igu r e 7. Thermal ellipsoid plot of the complex 5a (50%
probability level) with the labeling scheme. Selected bond
lengths (Å) and angles (deg): Au-C(1) ) 1.968(5), Au-Cl
) 2.2838(13), C(1)-C(2) ) 1.189(5), C(2)-C(3) ) 1.427(4),
C(10)-P(1) ) 1.698(2), C(10)-P(2) ) 1.702(2), P(1)-C(21)
) 1.805(2), P(1)-C(31) ) 1.810(2), P(1)-C(11) ) 1.817(2),
P(2)-C(61) ) 1.803(2), P(2)-C(51) ) 1.806(2), P(2)-C(41)
) 1.812(3); C(1)-Au-Cl ) 175.31(9), C(2)-C(1)-Au )
175.1(3), C(1)-C(2)-C(3) ) 178.8(4), P(1)-C(10)-P(2) )
128.60(13).
F igu r e 10. Thermal ellipsoid plot of the complex 6d ‚THF
(50% probability level) with the labeling scheme. Selected
bond lengths (Å) and angles (deg): Au-C(1) ) 1.999(2),
Au-C(9) ) 2.082(2), P(1)-C(9) ) 1.688(2), P(1)-C(21) )
1.814(2), P(1)-C(31) ) 1.819(2), P(1)-C(11) ) 1.834(2),
P(2)-C(9) ) 1.682(2), P(2)-C(41) ) 1.819(2), P(2)-C(61)
) 1.824(2), P(2)-C(51) ) 1.822(2), C(1)-C(2) ) 1.181(4),
C(2)-C(3) ) 1.437(4), C(6)-N ) 1.462(3), N-O(1) ) 1.222-
(3), N-O(2) ) 1.225(3); C(1)-Au-C(9) ) 174.36(9), C(2)-
C(1)-Au ) 168.9(2), C(1)-C(2)-C(3) ) 172.5(3), O(1)-N-
O(2) ) 123.1(2), O(1)-N-C(6) ) 118.2(2), O(2)-N-C(6)
) 118.7(2), P(2)-C(9)-P(1) ) 133.64(13), P(2)-C(9)-Au
) 110.66(11), P(1)-C(9)-Au ) 111.06(11).
F igu r e 8. Packing diagram showing C-H‚‚‚Au and three-
center C-H‚‚‚Cl interactions in complex 5a .
F igu r e 9. Thermal ellipsoid plot of the anion of complex
5c (50% probability level) with the labeling scheme. The
cation is numbered as for 5a . Selected bond lengths (Å)
and angles (deg): Au-C(1) ) 1.952(4), Au-Cl ) 2.2917-
(10), C(1)-C(2) ) 1.201(4), C(2)-C(3) ) 1.436(4), C(6)-O
) 1.370(3), O-C(9) ) 1.437(3), C(10)-P(1) ) 1.700(2),
C(10)-P(2) ) 1.703(2), P(1)-C(21) ) 1.796(2), P(1)-C(11)
) 1.810(2), P(1)-C(31) ) 1.811(2), P(2)-C(61) ) 1.804(2),
P(2)-C(41) ) 1.810(2), P(2)-C(51) ) 1.814(2); C(1)-Au-
Cl ) 174.66(7), C(2)-C(1)-Au ) 171.8(2), C(1)-C(2)-C(3)
) 175.5(3), C(6)-O-C(9) ) 115.83(19), P(1)-C(10)-P(2)
) 128.77(12).
F igu r e 11. Packing diagram showing C-H‚‚‚O interac-
tions in the complex 6d ‚THF.
173.20(14)-178.36(11)°). The Au-C bond length, 2.067-
(4) Å, is similar to Au-Cylide distances found in the other
complexes (3: 2.078(3), 2.074(3) Å; 6d , 2.083(2) Å; 8b,
2.079(3), 2.088(3) Å). The Au-Cl bond length (2.2914-
(10) Å) is similar to that found in complex 3 (2.2974(8)
Å). An intramolecular H(46)‚‚‚O(2) hydrogen bond
(2.25 Å) is observed. The molecules of 1b form dimers
through C-H‚‚‚O and C-H‚‚‚Cl hydrogen bonds and a
weak aurophilic interaction (H(33)‚‚‚O(1) ) 2.46 Å,
H(1)‚‚‚Cl(1) ) 2.56 Å, Au‚‚‚Au ) 3.5539(5) Å; see Figure
4). The dimers are connected by two further C-H‚‚‚O
interactions (H35‚‚‚O2 ) 2.53 Å, H23‚‚‚O2 ) 2.45 Å) to
form layers parallel to the plane (101) (see Figure 5).
There are several examples of these two different types
of interactions supporting the polymerization of gold
complexes.53
(see below). Eight hydrogen bonds of the type
C-H‚‚‚O, with H‚‚‚O distances in the range 2.39-2.57
Å, are observed in [4-MeC6H4S(O)2CH2PPh3]TfO; one
of the sulfone oxygens and the three triflate oxy-
gen atoms are each involved in two such hydrogen bonds
to form a layer parallel to the xz plane (see Figure 2).
The final sulfone oxygen O(1) forms a three-center
(C-H)2‚‚‚O system that connects adjacent layers.
In complex 1b the ligand arrangement around the
gold atom is essentially linear, with an C(1)-Au-Cl
bond angle equal to 178.36(11)° (Figure 3). This is a
common feature of all complexes here reported (range
In complex 3 (Figure 6), the Au‚‚‚Au distance is
3.1432(2) Å, a typical value for an aurophilic contact

5898 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
The structure of complexes 5a (Figures 7 and 8) and
5c (Figure 9), which are isostructural, show the ylide
cation [HC(PPh3)2]+ and the anionic gold complex. The
Cl-Au-C(1), Au-C(1)-C(2), and C(1)-C(2)-C(3) bond
angles are near 180° (range 171.8(2)-178.8(4)°). The
Au-Cl bond distance in 5a (2.2838(13) Å) is, unexpect-
edly, shorter than that in 5c (2.2917(10) Å). The latter
is similar to those found in complexes 1b and 3. The
Au-C(1) distances in 5a and 5c are similar (1.968(5)
and 1.952(4) Å, respectively) but significantly shorter
than that found in the alkynyl complex 6d (1.998(2) Å).
However, all these distances are in the range found in
other neutral and anionic alkynyl gold(I) complexes
(1.972(8)-2.080(12) Å),19,51,54 although that of 5c estab-
lishes a new minimum in this range. The C(1)-C(2) and
C(2)-C(3) bond distances in 5a , 5c, and 6d are not
significantly different.
In compounds 5a and 5c, the packing shows broad
chains of anions and cations parallel to the z axis,
connected by a short C-H‚‚‚Au contact (H(7)‚‚‚Au )
2.91 Å; values apply to 5a ) between anions and a three-
center (C-H)2‚‚‚Cl system (H(44,45)‚‚‚Cl ) 2.83 and
2.98 Å) between anion and cation (Figure 8). The
chains are linked by a further C-H‚‚‚Cl interaction
(H(24)‚‚‚Cl ) 2.84 Å) to form the final three-dimensional
structure.
Most of the structural data on complexes 6d (Figures
10 and 11) and 8b (Figures 12 and 13) have been
discussed above. The only reported crystal structures
of C(PPh3)2 complexes are those of [Ni(CO)n{C(PPh3)2}]
(n ) 2, 3),40 [CuX{C(PPh3)2}] (X ) Cl, Cp*),29,41 and
[O3Re{C(PPh3)2}][ReO4].42 The P-C bond distances in
complex 6d (Figure 10) (1.688(2), 1.682(2) Å) are in the
range 1.66-1.70 Å found in the above Ni(0) and Cu(I)
complexes but longer than those in the free ylide
C(PPh3)2 (1.610-1.633 Å).55 The significant double
character of the Re-C(PPh3)2 bond in [O3Re{C(PPh3)2}]-
[ReO4], as a consequence of the π-donor capacity of the
ylide, is consistent with the longest P-C bond distances
(1.777(8), 1.764(8) Å).42 However, the P-C-P angles do
not generally follow the expected increase when the
P-C bond order increases. Thus, the expected order
should be C(PPh3)2 > 6d ≈ Ni(0) and Cu(I) complexes
> [O3Re{C(PPh3)2}][ReO4] but the actual order is
C(PPh3)2 (130.1-143.8°) g [Cu(Cp*){C(PPh3)2}] (135.97°)
≈ 6d (133.71°) ≈ [Ni(CO)2{C(PPh3)2}] (132.13°) > [Ni-
(CO)3{C(PPh3)2}] (124.58°) ≈ [CuCl{C(PPh3)2}] (123.8°)
≈ [O3Re{C(PPh3)2}][ReO4] (123.1°). A theoretical study
on [Ni(CO)3{C(PH3)2}] gives an excellent agreement
between the calculated (124.6°) and the experimental
value of the P-C-P angle in [Ni(CO)3{C(PPh3)2}]
(124.58°).40 However, the calculated value in [Ni(CO)2-
{C(PH3)2}] (126.6°) is lower than the experimental one
for [Ni(CO)2{C(PPh3)2}] (132.13°). No explanation was
given. Charge decomposition analysis of these Ni com-
plexes shows that carbodiphosphoranes are much better
σ donors than π acceptors and that this component is
more important for [Ni(CO)2{C(PH3)2}] than for [Ni-
(CO)3{C(PH3)2}].40 Because the P-C-P angles and P-C
bond distances in [Ni(CO)2{C(PPh3)2}] and in 6d are
F igu r e 12. Thermal ellipsoid plot of the complex 8b (50%
probability level) with the labeling scheme. Selected bond
lengths (Å) and angles (deg): Au-C(2) ) 2.079(3), Au-
C(1) ) 2.088(3), S(1)-O(2) ) 1.440(2), S(1)-O(1) ) 1.446-
(3), S(1)-C(11) ) 1.763(4), S(1)-C(1) ) 1.782(4), S(2)-O(4)
) 1.441(2), S(2)-O(3) ) 1.444(3), S(2)-C(51) ) 1.763(4),
S(2)-C(2) ) 1.791(4), P(1)-C(1) ) 1.798(4), P(2)-C(2) )
1.805(4); C(2)-Au-C(1) ) 173.20(14), O(2)-S(1)-O(1) )
117.02(17), C(11)-S(1)-C(1) ) 101.27(19), O(4)-S(2)-O(3)
) 117.04(17), C(51)-S(2)-C(2) ) 101.50(19), S(1)-C(1)-
P(1) ) 119.0(2), S(1)-C(1)-Au ) 108.13(17), P(1)-C(1)-
Au ) 113.0(2), S(2)-C(2)-P(2) ) 117.77(19), S(2)-C(2)-
Au ) 108.61(17), P(2)-C(2)-Au ) 114.2(2).
F igu r e 13. Packing diagram showing intermolecular
hydrogen bond interactions in 8b.
supported by a bridging carbon donor ligand.10 However,
shorter Au‚‚‚Au distances have been found in similar
but cationic complexes (2.7999(7)-3.008(1) Å).13,30,31,32a,b,33
Correspondingly, the Au(1)-C(1)-Au(2) angle (98.44-
3
(11)°) is narrower than expected for two Csp hybrid
orbitals. The P(1)-C(1) and P(2)-C(1) bond lengths are
equal (1.776(3) Å) and shorter than P-Ph distances
(1.809(3)-1.825(3) Å), showing a certain multiple char-
acter of the bonds in the P(1)-C(1)-P(2) group; in
3
phosphonium salts P-Csp and P-Ph distances tend to
be around 1.800 Å.54 As indicated above, the electron
density for such an increase in bond order probably
comes from the gold atoms. The P(1)-C(1)-P(2) angle
in 3 is 117.30(15)°, a value approaching that corre-
2
sponding to two Csp hybrid orbitals.
The packing of complex 3 involves 13 C-H‚‚‚Cl
contacts, a number promoted in part by the presence of
three ordered dichloromethane molecules, and shows no
easily assimilable features such as layers or chains.
(53) Mingos, D. M. P.; Yau, J .; Menzer, S.; Williams, D. J . J . Chem.
Soc., Dalton Trans. 1995, 319. Vicente, J .; Chicote, M.-T.; Abrisqueta,
M.-D.; Guerrero, R.; J ones, P. G. Angew. Chem., Int. Ed. Engl. 1997,
36, 1203. Vicente, J .; Chicote, M. T.; Guerrero, R.; Saura-Llamas, I.
M.; J ones, P. G.; Ram´ırez de Arellano, M. C. Chem. Eur. J . 2001, 7,
638. Hollatz, C.; Schier, A.; Schmidbaur, H. J . Am. Chem. Soc. 1997,
119, 8115. Tzeng, B. C.; Schier, A.; Schmidbaur, H. Inorg. Chem. 1999,
38, 3978. Ahrens, B.; J ones, P. G.; Fischer, A. K. Eur. J . Inorg. Chem.
1999, 1103.
(54) Vicente, J .; Chicote, M. T.; Abrisqueta, M. D.; J ones, P. G.
Organometallics 2000, 19, 2629.
(55) Hardy, G. E.; Zink, J . I.; Kaska, W. C.; Baldwin, J . E. J . Am.
Chem. Soc. 1978, 100, 8001. Vincent, A. T.; Wheatley, P. J . J . Chem.
Soc., Dalton Trans. 1972, 617.

Ylide-, Alkynyl-, and Alkynyl/ Ylide-Gold(I) Complexes
Organometallics, Vol. 21, No. 26, 2002 5899
very similar, it is reasonable to asume that the M-C-
(PPh3)2 bonds are analogous in both complexes.
Hydrogen bond interactions involving C-H of the
phenyl groups of the ligand PPh3 and the oxygen atoms
of the nitro group, which both accept two H bonds
(H‚‚‚O ) 2.34-2.62 Å), link the molecules in a three-
dimensional network (Figure 11). The H bonds involving
the nitro group occupy the regions at z ≈ 0, 1, etc., with
each molecule displaying donor and acceptor functions
separated by a translation of approximately c. The THF
oxygens are also acceptors of two C-H‚‚‚O hydrogen
bonds (H‚‚‚O ) 2.53, 2.62 Å).
In 8b there are two very short intramolecular
C-H‚‚‚O hydrogen bonds involving two ortho hydrogens
(H(26)‚‚‚O(1) ) 2.30 Å and H(76)‚‚‚O(3) ) 2.26 Å) groups
(Figure 13) of PPh3 and two oxygen atoms of the SO2
groups. In addition, two intermolecular hydrogen bonds
from para hydrogens (H(84)‚‚‚O(2) ) 2.37 Å and
H(44)‚‚‚O(4) ) 2.55 Å) connect the cations to form chains
parallel to the diagonal [1,0,-1].
1b, 7, and 8b (4.58-5.32 ppm) is intermediate between
that of the ylide (2.96 ppm) and that corresponding to
the methylene protons of [4-MeC6H4S(O)2CH2PPh3]I
(6.18 ppm). The same behavior has been observed in
other gold complexes with carbonyl-stabilized ylides.30,31
The same order is observed for the δ(1H) value of the
methine proton of the ylide cation [HC(PPh3)2]+ (1.86-
1.93 ppm in complexes 5, 1.83 ppm in [HC(PPh3)2]Br,
and 1.86 ppm in [HC(PPh3)2]TfO) < that in complexes
2 and 8 (5.58, 5.69 ppm) < that in the methylene protons
of the phosphonium salt [CH2(PPh3)2](TfO)2 (6.30 ppm).
Therefore, replacement of a proton in a phosphonium
salt by a gold moiety increases the shielding of the
remaining methine proton. This is in agreement with
the conclusion we have reached from the IR spectra (see
above).
The δ(31P) values tend to follow a different order:
ylide 4-MeC6H4S(O)2CHPPh3 (14.8 ppm) < [4-MeC6H4S-
(O)2CH2PPh3]I (17.6 ppm) < complexes 1b, 7, and 8b
(20.2-21.8 ppm). The same order is followed by the
δ(31P) values of the ylide C(PPh3)2 (-3.5 ppm)57 < the
ylide cation [HC(PPh3)2]+ (21.1 ppm in complexes 5) <
complexes 1a , 4, and 6 (14.3-16.6 ppm). The same
series was observed with the ylide Me2NC(O)CHPPh3
with respect to some [Me2NC(O)CH2PPh3]+ salts and a
series of its gold complexes, although not then appreci-
ated at the time.33 However, a different sequence is
found for the ylide cation [HC(PPh3)2]+ (21.1 ppm in
complexes 5 and the bromide and triflate salts),
which is very similar to that of its phosphonium
salts [CH2(PPh3)2]X (X ) Br, 20.99 ppm; X ) TfO,
20.47 ppm), although both are smaller than the δ(31P)
values in its complexes 2 and 8a (22.1, 26.1 ppm,
respectively).
Sp ectr oscop ic P r op er ties of Com p lexes. The ylide
4-MeC6H4SO2CHPPh3 shows two strong bands at
1270 and 1126 cm-1 that have been assigned to
ν
asym(SO2) and νsym(SO2) modes, respectively.52 The salts
[4-MeC6H4S(O)2CH2PPh3]X (X ) I, TfO) show these
bands at higher energy (1342-1324 and 1160-1156
cm-1, respectively) in agreement with the assignments
made for the bromide salt (1330 and 1165 cm-1
,
respectively).52 This shift to higher energy of these
bands can be explained as a consequence of the contri-
bution of resonance forms C and D, which cannot be
formulated for the phosphonium salt, to the electronic
structure of the ylide (Chart 1). In aryl/alkyl sulfones,
two bands in the ranges 1334-1325 and 1160-1150
cm-1 have been assigned to the νasym(SO2) and νsym(SO2)
modes, respectively.56 However, Zhdankin has assigned
a band at 1441 cm-1 to ν(SdO) in [PhS(O)2CH2PPh3]-
TfO.48
Con clu sion s
We have prepared the first complexes containing
the ylide 4-MeC6H4SO2CHPPh3 or the ylide cation
[HC(PPh3)2]+ and some of the few complexes containing
the double ylide C(PPh3)2. To prepare the alkynyl-ylide
complexes [Au(CtCR)(ylide)] (we wanted to study their
NLO properties), we have studied the reactivity of the
corresponding [AuCl(ylide)] complexes toward terminal
alkynes in the presence Et3N. This method was suc-
cessful for the synthesis of the complexes [Au(CtCR)-
{CH(PPh3){S(O)2C6H4Me-4}}], but when the ylide was
C(PPh3)2, the complexes [HC(PPh3)2][Au(CtCR)Cl] were
obtained. To synthesize the desired alkynyl-ylide com-
plexes [Au(CtCC6H4R-4){C{PPh3}2}], we prepared [Au-
(acac){C(PPh3)2}] and studied its reactivity toward
alkynes by NMR spectroscopy. We concluded that a
large excess of the alkyne (ca. 1:25-30) and 1-4 h of
reaction is required to obtain the pure compounds with
good yields. The tri- and monocationic complexes [Au-
(ylide)2](TfO)n, where the ylide is [HC(PPh3)2]+ (n ) 3)
or 4-MeC6H4S(O)2CHPPh3 (n ) 1), have been obtained
by reacting PPN[Au(acac)2] with the corresponding
phosphonium salt. IR and NMR criteria have been
established to prove the C-coordination of the ylide
4-MeC6H4S(O)2CHPPh3. The crystal structures of some
of the reported complexes show interesting aurophilic
When the IR spectra of complexes differing only in
the ylide ligand are compared (e.g., 1a with 1b, 6a with
7a , etc.), those containing the sulfonylylide ligand show
a strong band at around 1300 (s) (see the Experimental
Section), usually appearing with two shoulders at lower
and higher energies, and a medium or strong band in
the range 1138-1124 cm-1, which could be assigned to
νasym(SO2) and νsym(SO2), respectively. The lower values
of the wavenumbers of these bands with respect to those
of in the phosphonium salts suggest that metallic
substituents at the methine group (X in Chart 1) are
more electron-releasing than a hydrogen. This conclu-
sion was also reached when studying the IR spectra of
gold complexes of carbonyl-stabilized ylides.31
Because the assigned ν(SO2) bands appear in regions
where other bands are present, IR spectroscopy is not
as useful as in the case of carbonyl-stabilized ylides to
indicate the mode of coordination of the ligand. In our
case, the determination of the crystal structure of
complexes 1b and 8b, along with the use of NMR
spectroscopy, allows us to propose the C-coordination
of the sulfonylylide ligand in all complexes. Thus, the
1H NMR resonance of the methine proton in complexes
(56) Bellamy, L. J . The Infrared Spectra of Complex Molecules;
Chapman and Hall: New York, 1980; Vol. 2 (Advances in Infrared
Group Frequencies).
(57) Ramirez, F.; Pilot, J . F.; Desai, N. B.; Smith, C. P.; Hansen, B.;
McKelvie, N. J . Am. Chem. Soc. 1967, 89, 6273.

5900 Organometallics, Vol. 21, No. 26, 2002
Vicente et al.
interactions and/or hydrogen bond interactions. Two of
these crystal structures are the first gold complexes
containing the ligand C(PPh3)2.
istry, Australian National University, Canberra, Aus-
tralia, for samples of some acetylenes.
Su p p or tin g In for m a tion Ava ila ble: Listings of all re-
fined and calculated atomic coordinates, anisotropic thermal
parameters, and bond lengths and angles for [4-MeC6H4S(O)2-
CH2PPh3]TfO, 1b‚0.5CH2Cl2, 3‚3CH2Cl2, 5a , 5c, 6d ‚THF, and
8b. This material is available free of charge via the Internet
at http://pubs.acs.org.
Ack n ow led gm en t. We thank the Ministerio de
Educacion, Cultura y Deporte (Grant SB99 A2657591
to A.R.S.), the Ministerio de Ciencia y Tecnolog´ıa,
FEDER (Grant No. BQU2001-0133), and the Fonds der
Chemischen Industrie for financial support and Steph
Hurst and Clem Powell from the Department of Chem-
OM020753P