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R. Contreras et al. / Journal of Organometallic Chemistry 689 (2004) 395–404
2. Experimental
2.1. General
3.07 [s, 2H, Hanti], 3.90 [s, 2H, Hsyn], 7.46 [dt, 1H, H4,
3J(H4–H5) ¼ 3J(H4–H3) ¼ 7.45 Hz, 4J(H4–H6) ¼ 1.3 Hz],
7.52 [dt, 1H, H5, 3J(H5–H4) ¼ 3J(H5–H6) ¼ 7.45 Hz,
3
4J(H5–H3) ¼ 1.4 Hz], 7.60 [pt, 2H, H9, H11, J(H9–H8)
3
3
All reactions were carried out under purified nitrogen
by using Schlenk-tube techniques. The solvents used in
the reactions were of analytical grade and, in some cases
of reagent grade, and were dried by a reported proce-
dure [9]. The 2-(methylthio)-N-substituted-benzylidene)
anilines were synthesised according to standard proce-
dures by condensing equimolar amounts of 2-(methyl-
thio)aniline and the respective substituted benzaldehyde,
under continuous stirring for 2 h, in the presence of
magnesium sulfate [10]. The compounds [(g3-Me-al-
lyl)Pd(l-X)]2 (X ¼ Cl, I) [11,12] and [(EtO)2PS2K] [13]
were prepared following literature methods.
NMR spectra were recorded on Bruker AC-200P and
Avance-400 spectrometers. Chemical shifts are reported
in ppm relative to Me4Si (1H) and 85% H3PO4
(31P{1H}, positive shifts downfield). The IR spectra in
the range 4000–250 cmꢀ1 were recorded in KBr pellets
on a model Vector-22 FT-IR Bruker spectrophotometer.
Elemental analyses (C, H, N, S) were made with a Fi-
sons model EA-1108 microanalyser. FAB mass spectral
analyses were performed in a VG Autospec spectrome-
ter with 3-nitrobenzylalcohol as a matrix. Conductivity
measurements were carried out in solution, using a
WTW LF-521 conductimeter with a cell of constant
1.07.
ꢁ
3J(H9–H11) ꢁ J(H11–H10) ꢁ J(H11–H12) ¼ 7.5 Hz],
7.74–7.65 [m, 3H, H10, H6, H3], 8.06 [d, 2H, H8, H12,
3
3J(H8–H12) ꢁ J(H12–H11) ¼ 7.3 Hz], 9.09 [s, 1H, CH7@
N]. FT-IR (KBr, cmꢀ1): m(CN), 1610 vs, m(BF4), 1057 vs,
521 m. MS (FABþ) m/z 388 (Mþ–BF4).
2: Yield: 198 mg (79%). Anal. Found: C, 43.9; H, 4.1;
S, 6.3; N, 2.6. Calc. for C18H19BF5NPdS: C, 43.8; H,
3.8; S, 6.5; N, 2.8%. KM ¼ 112.8 Xꢀ1 molꢀ1 cm2. H
1
NMR in CD3CN; d 2.04 [s, 3H, C(allyl)–Me], 2.83 [s,
3H, S–Me], 3.07 [s, 2H, Hanti], 3.96 [s, 2H, Hsyn], 7.34
[dd, 1H, H11, 3J(H11–H10) ¼ 9.3 Hz, 4J(H11–H9) ¼ 1.6
Hz] 7.43 [dd, 1H, H8, 3J(H8–H9) ¼ 7.4 Hz, 4J(H11–
H9) ¼ 1.9 Hz], 7.50 [m, 2H, H3, H4], 7.64 [m, 2H, H5,
3
H6], 7.74 [dpt, 1H, H10, 3J(H10–H11) ꢁ J(H10–H9) ꢁ 7.4
Hz, 4J(H10–H8) ¼ 1.9 Hz], 8.21 [dt, 1H, H9, 3J(H9–
3
H8) ꢁ J(H9H10) ¼ 7.5 Hz], 9.18 [s, 1H, CH7@N].19F
NMR in CD3CN: d )115.8 [s, F-ring]. FT-IR (KBr,
cmꢀ1): m(CN), 1621 vs, m(BF4), 1060 vs, 521 m. MS
(FABþ) m/z 406 (Mþ–BF4).
3: Yield: 168 mg (65%). Anal. Found: C, 46.4; H, 4.7;
S, 6.3; N, 3.1. Calc.for C19H22 BF4NPdS: C, 46.6; H,
4.5; S, 6.5; N, 2.9%. 1H NMR in CD3CN: d 2.02 [s, 3H,
C(allyl)–Me], 2.57 [s, 3H, C–Me], 2.91 [s, 3H,S–Me],
2.02 [s, 2H, Hanti], 3.85 [s, 2H, Hsyn], 7.41 [d, 1H, H11,
3J(H11–H10) ¼ 8.2 Hz], 7.43 [pt, 1H, H9, 3J(H9–
3
H8) ꢁ J(H9–H10) ¼ 8.1 Hz], 7.56 [m, 3H, H4, H5, H10],
4
2.2. Synthesis of complexes
7.75 [dd, 1H H3, 3J(H3–H4) ¼ 7.5 Hz, J(H3–H5) ¼ 1.5
Hz], 7.78 [dd, 1H, H6, 3J(H6–H5) ¼ 7.5 Hz, 4J(H6–
H4) ¼ 1.3 Hz], 7.95 [d, 1H, H8, 3J(H8–H9) ¼ 7.6 Hz],
9.37 [s, 1H, CH7@N]. FT-IR (KBr, cmꢀ1): m(CN), 1610
vs, m(BF4), 1056 vs, 521 m. MS (FABþ) m/z 402 (Mþ–
BF4).
2.2.1. [(g3-Me-allyl)Pd(g2-S,N-MeSC6H4N@CHC6H4
(X)Y)]BF4 [X ¼ H, Y ¼ H (1); X ¼ F, Y ¼ H (2);
X ¼ Me, Y ¼ H (3); X ¼ H, Y ¼ Cl (4); X ¼ H,
Y ¼ Me2N (5); X ¼ H, Y ¼ NO2 (6)]
A solution of [(g3-Me-allyl)Pd(l-Cl)]2 (0.25 mmol,
100 mg) in THF (20 cm3) was treated with AgBF4 (0.51
mmol, 100 mg). The mixture was stirred at room tem-
perature for 2 h and the AgCl formed was filtered off
through Kieselguhr. To the resulting solution was added
a stoichiometric amount of the corresponding bidentate
ligand [L1: 0.50 mmol, MeSC6H4N@CHC6H5 (113.5
mg); MeSC6H4N@CHC6H4F (122.5 mg); MeSC6H4N@
CHC6H4Me (120.5 mg); MeSC6H4N@CHC6H4Cl
(130.8 mg); MeSC6H4N@CHC6H4NMe2 (135 mg);
MeSC6H4N@CHC6H4NO2 (136 mg)], and the mixture
stirred at room temperature. The solution was concen-
trated to a small volume and the complexes were pre-
cipitated by the addition of Et2O. The solid product was
collected by filtration, washed with cold THF and Et2O,
and dried under vacuum.
4: Yield: 168 mg (65%). Anal. Found: C, 41.3; H, 3.6;
S, 6.2; N, 2.7. Calc. for C18H19BClF4NPdS: C, 41.1; H,
3.6; S, 6.1; N, 2.6%. 1H NMR in CD3CN; d 2.08 [s, 3H,
C(allyl)–Me], 2.88 [s, 3H, S–Me], 3.11 [s, 2H, Hanti], 3.97
3
[s, 2H, Hsyn], 7.49 [dt, 1H, H4, 3J(H4–H3) ꢁ J(H4–
H5) ¼ 7.5 Hz; 4J(H4–H6) ¼ 1.3 Hz], 7.54 [dt, 1H, H5,
3
4
3J(H5–H4) ꢁ J(H5–H6) ¼ 7.6 Hz, J(H5–H3) ¼ 1.5 Hz],
7.63 [d, 2H, 0 Hb,Hb0, AA0BB0 system: 3J(Ha–
Hb) ¼ 3J(Ha0-Hb ) ¼ 8.5 Hz], 7.69 [dd, 1H, H3, J(H3–
3
H4) ¼ 7.6 Hz, 4J(H3–H5) ¼ 1.5 Hz], 7.74 [dd, 1H, H6,
3J(H6–H5) ¼ 7.6 Hz, J(H6–H4) ¼ 1.2 Hz], 8.07 [d, 2H,
4
Ha, Ha0, AA0BB0 system: 3J(HaHb) ¼ 3J(Ha0–Hb0) ¼ 8.5
Hz], 9.07 [s, 1H, CH7@N]. FT-IR (KBr, cmꢀ1): m(CN),
1612 vs, m(BF4), 1060 vs, 521 m.
5: Yield: 253 mg (96%). Anal. Found: C, 46.2; H, 4.8;
S, 6.3; N, 5.4. Calc. for C20H25BF4N2PdS: C, 46.3; H,
4.9; S, 6.2; N, 5.4%. 1H NMR in CD3CN: d 2.21 [s, 3H,
C(allyl)–Me], 2.86 [s, 3H, S–Me], 3.13 [s, 6H, NMe2],
3.18 [s, 2H, Hanti], 4.07 [s, 2H, Hsyn], 6.85 [d, 2H, Hb,Hb0,
AA0BB0 system: 3J(Ha–Hb) ¼ 3J(Ha0–Hb0) ¼ 9.0 Hz],
1: Yield: 200 mg (83%). Anal. Found: C, 45.7; H, 4.3;
S, 6.5; N, 2.5. Calc. for C18H20BF4NPdS: C, 45.5; H, 4.2;
S, 6.7; N, 2.9%. KM ¼ 200 Xꢀ1 molꢀ1cm2. H NMR in
1
CD3CN: d 2.07 [s, 3H, C(allyl)–Me], 2.85 [s, 3H, S–Me],