Synthesis of [PdCl(Me,Me-Phebox)] (12)
2 Grignard Reagents, New Developments, ed. H. G. Richey, Wiley,
Chichester, UK, 2000.
3 (a) C. Eaborn, K. J. Odell and A. Pidcock, J. Chem. Soc., Dalton Trans.,
1979, 1288; (b) R. Uso´n, J. Vicente, J. A. Cirac and M. T. Chicote,
J. Organomet. Chem., 1980, 198, 105; (c) M. Hu¨ttenhofer, A. Weeber
and H. H. Brintzinger, J. Organomet. Chem., 2002, 663, 58.
4 (a) F. Cicogna, B. Gaddi, G. Ingrosso, M. Marcaccio, F. Marchetti, D.
Paolucci, F. Paolucci, C. Pinzino and R. Viglioni, Inorg. Chim. Acta,
2004, 357, 2915; (b) F. Bertini, L. Calucci, F. Cicogna, B. Gaddi, G.
Ingrosso, M. Marcaccio, F. Marchetti, D. Paolucci, F. Paolucci and
C. Pinzino, J. Organomet. Chem., 2006, 691, 2987; (c) R. Bhawmick,
P. Das, D. N. Neogi and P. Bandyopadhay, Polyhedron, 2006, 25,
1177.
5 (a) V. I. Sokolov and O. A. Reutov, Coord. Chem. Rev., 1978, 27, 89;
(b) J. Vicente, M. T. Chicote, A. Arcas, M. Artigao and R. Jime´nez,
J. Organomet. Chem., 1983, 247, 123; (c) H. C. L. Abbenhuis, M.
Pfeffer, J. P. Sutter, A. Decian, J. Fischer, H. L. Li and J. H. Nelson,
Organometallics, 1993, 12, 4464; (d) J. Vicente, J. A. Abad, J. Gil-Rubio,
P. G. Jones and E. Bembenek, Organometallics, 1993, 12, 4151; (e) M.
Pfeffer, J. P. Sutter and E. P. Urriolabeitia, Inorg. Chim. Acta, 1996,
249, 63; (f) J. Vicente, J. A. Abad, B. Rink, F.-S. Herna´ndez and M. C.
Ram´ırez de Arellano, Organometallics, 1997, 16, 5269; (g) R. V. Parish,
J. P. Wright and R. G. Pritchard, J. Organomet. Chem., 2000, 596,
165; (h) A. Berger, A. Decian, J. P. Djukic, J. Fischer and M. Pfeffer,
Organometallics, 2001, 20, 3230; (i) Y. J. Wu, L. R. Yang, X. L. Cui,
C. X. Du and Y. Zhu, Tetrahedron: Asymmetry, 2003, 14, 1073; (j) J. P.
Djukic, M. Duquenne, A. Berger and M. Pfeffer, Inorg. Chim. Acta,
2006, 359, 1754.
In air, a solution of 9 (218.5 mg, 0.15 mmol) in toluene (15 mL)
was added to a solution of [PdCl2(SEt2)2] (107 mg, 0.3 mmol) in
toluene (5 mL). The flask was rinsed with an additional portion
of toluene (3 mL). The reaction mixture was stirred overnight
after which it was centrifuged and separated. The residue was
extracted with 6 mL toluene. After removal of the solvent the
residue was characterized as pure 3 (146.7 mg, 100%) Anal. Calcd
for C36H28Au2Cl2P2: C, 43.79; H, 2.86; Found: C, 43.93; H, 2.76.
The mother liquor was evaporated to afford 12 (122 mg, 100%) as
an air stable light yellow solid. 1H NMR (C6D6, 300 MHz): d 1.49
3
(s, 12H), 3.60 (s, 4H), 6.67 (t, 1H, JH–H = 7.7 Hz), 7.05 (d, 2H,
1
3JH–H = 7.8 Hz). 13C{ H} NMR (C6D6, 75 MHz): d 27.9, 66.0, 82.8,
123.7, 126.5, 130.7, 169.2, 172.5. Anal. Calcd for C16H19ClN2O2Pd:
C, 46.51; H, 4.63; N, 6.78; Found: C, 46.42; H, 4.69; N, 6.63.
Crystal structure determination of [(Au(NCN))2(dppbp)] (6)
C60H66Au2N4P2·C7H8, Mr = 1391.18, colorless, irregular crystal
cut from a larger aggregate (approximate dimensions 0.2 ×
¯
0.3 × 0.3 mm), triclinic, space group P 1 (no. 2) with a =
˚
10.6883(10), b = 11.8062(10), c = 13.7445(10) A, a = 104.35(3),
◦
3
6 (a) J. W. Lauher and K. Wald, J. Am. Chem. Soc., 1981, 103, 7648;
(b) H. Kudo, Nature, 1992, 355, 432.
˚
b = 90.04(4), c = 115.51(4) , V = 1505.0(2)A , Z = 1, l(Mo-
Ka) = 4.964 mm−1. 43 053 Reflections were measured, 6878 of
which were independent, Rint = 0.0423, Rr = 0.0243, 1.54◦ < h <
27.45◦, T = 150 K, Mo-Ka radiation, graphite monochromator,
7 For leading references on the synthesis of arylgold(I) complexes see:
(a) H. Schmidbauer, A. Grohmann, M. E. Olmos and A. Schier, in
Organic Derivatives of Gold and Silver, ed. S. Patai and Z. Rappoport,
Wiley, Chichester, UK, 2003, ch. 8, Synthesis and Uses of Organogold
Compounds, pp. 227–311; (b) E. J. Fernandez, A. Laguna and E. M.
Olmos, Adv. Organomet. Chem., 2005, 52, 77.
8 M. Contel, M. Stol, M. A. Casado, G. P. M. van Klink, D. D. Ellis,
A. L. Spek and G. van Koten, Organometallics, 2002, 21, 4556.
9 S. S. Elmorsy, A. Pelter and K. Smith, Tetrahedron Lett., 1991, 32,
4175.
10 Appeared in literature while we were working on this subject: P.
Sevillano, T. Langetepe and D. Fenske, Z. Anorg. Allg. Chem., 2003,
629(2), 207.
11 P. Steenwinkel, D. M. Grove, N. Veldman, A. L. Spek and G. van
Koten, G., Organometallics, 1998, 17, 5647.
12 M. Stol, M. Lutz, A. L. Spek, G. P. M. van Klink and G. van Koten,
Manuscript in preparation.
13 J. G. Donkervoort, J. T. B. H. Jastrzebski, B.-J. Deelman, H. Kooijman,
N. Veldman, A. L. Spek and G. van Koten, Organometallics, 1997, 16,
4174.
14 (a) M. A. Stark, G. Jones and C. J. Richards, Organometallics, 2000,
19, 1282; (b) M. A. Stark and C. J. Richards, Tetrahedron Lett., 1997,
38, 5881.
15 J. S. Fossey and C. J. Richards, Organometallics, 2004, 23, 367.
16 S. E. Denmark, R. A. Stavenger, A.-M. Faucher and J. P. Edwards,
J. Org. Chem., 1997, 62, 3375.
˚
k = 0.71073 A. Data were collected on a Nonius Kappa CCD
area detector on rotating anode and corrected for absorption
by a multi-scan method (PLATON/MULABS,19 T-range 0.238–
0.368). The structure was solved by Patterson methods (DIRDIF-
99)20 and refined on F2 using SHELXL-97-2.21 The unit cell
contains a toluene molecule, disordered over a crystallographic
inversion centre. Mild distance restraints were applied to enforce
a reasonable geometry of the solvent molecule. Hydrogen atoms
were included in the refinement on calculated positions riding on
their carrier atoms. All non-hydrogen atoms were refined with
anisotropic displacement parameters. Hydrogen atom displace-
ment was described with a fixed isotropic parameter linked to
the value of the equivalent isotropic parameter of their carrier
atoms. Final wR2 ( = {R [w(Fo − Fc )2]/R [w(Fo2)2]}1/2) = 0.0527,
2
2
w = 1/[r2(Fo2) + (0.0253P)2 + 1.20P], where P = (max(Fo2,0) +
2
2Fc )/3, R1 ( = R ꢁFo| − |Fcꢁ/R |Fo| ) = 0.0208 (for 6469 I >
−3
˚
2r(I)), S = 1.088, 336 refined parameters, −1.32 < Dq < 1.04 e A
(near Au).
17 R. Uso´n, A. Laguna and M. Laguna, Inorg. Synth., 1989, 26, 85.
18 M. Stol, D. J. M. Snelders, J. J. de Pater, H. Kooijman, A. L. Spek,
G. P. M. van Klink and G. van Koten, Organometallics, 2005, 24, 743.
19 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7.
CCDC reference numbers 254665 for compound 6.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b701271c
20 P. T. Beurskens, G. Beurskens, R. de Gelder, S. Carc¸ia-Granda, R. O.
Gould, R. Israel and J. M. M. Smits, The DIRDIFF99 Program
System, Technical Report of the Crystallography Laboratory, University
of Nijmegen, The Netherlands.
References
1 B. J. Wakefield, Best Synthetic Methods, Organolithium Methods,
Academic Press, London, 1988.
21 G. M. Sheldrick, SHELXL-97. Program for Crystal Structure Refine-
ment, University of Go¨ttingen, Germany, 1997.
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The Royal Society of Chemistry 2007
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