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L. Cano6ese et al. / Journal of Organometallic Chemistry 566 (1998) 61–71
5.2.4. [Pd(p3-1,1-Me2C3H3)(C5H4N-2-CH2SC6H5)]ClO4
(1c)
5.3. Preparation of Pd(0) complexes
Yield 87% (white microcrystals). Found: C 43.01; H
4.18; N 3.03; S 6.81. C17H20NSO4ClPd requires C
42.87; H 4.23; N 2.94; S 6.73%. IR: w(CN) 1606; w(ClO)
5.3.1. [Pd(p2-(CHCN)2)(C5H4N-2-CH2SC(CH3)3)] (2d)
To a solution of (2-(tert-butylthiomethyl)pyridine)
(0.083 g, 0.46 mmol) in anhydrous acetone (10 cm3),
Pd2DBA3C CHCl3 (0.215 g, 0.21 mmol) and fn (0.0357
g, 0.45 mmol) were added under nitrogen. The initial
dark suspension of reagents slowly dissolved (1.5 h)
giving a yellowish solution. Addition of activated char-
coal and filtration on celite removed metallic palladium
yielding a bright yellow solution. Reduction to small
volume (3–4 cm3) and addition of diethyl ether (15
cm3) gave a pale yellowish precipitate which was filtered
off and washed with diethyl ether in excess to remove
the DBA (the resulting washing solvent was colorless).
The microcrystals were dried under reduced pressure
and stored under inert atmosphere (0.127 g, 87%).
Found: C 45.85; H 4.61; N 11.52; S 8.91. C14H17N3SPd
requires C 45.97; H 4.68; N 11.49; S 8.76%. IR:w(CN)
2195 (fn): w(CN) 1597 (pyridine ring) cm−1 (KBr pellet).
1
1103: l(ClO) 623 cm−1 (KBr pellet). H-NMR (CD2Cl2
298 K): l(ppm) 1.29 (D1,CH3anti: bs), 1.54 (D2,CH3anti
:
bs); 1.67 (D1,CH3syn: bs), 1.83 (D2,CH3syn: bs); 3.92 (D1,
Hanti: bs), 3.37 (D2, Hanti: bs); 4.45 (D1, Hsyn: bs),4.20
(D2, Hsyn: bs); 4.70 (D1+D2,CH6 2–S:bs); 5.63 (D1+D2,
H2(allyl): bs); 7.38–7.55 (D1+D2,H(phen)+H5(pyr): m); 7.63
(D1+D2, H3(pyr): d, J=7.8); 7.98 (D1+D2, H(4pyr): t,
J=7.8); 8.84 (D1, H6(pyr): bs); 8.55 (D2, H(6pyr): bs).
5.2.5.
[Pd(p3-2-MeC3H4)(C5H4N-2-CH2SC(CH3)3)]ClO4 (1e)
Yield 92% (white microcrystals). Found: C 38.13; H
4.95; N 3.22; S 7.30. C14H22NSO4ClPd requires C
38.02; H 5.01; N 3.17; S 7.25%. IR: w(CN) 1603; w(ClO)
1
1090; l(ClO) 623 cm−1 (KBr pellet). H-NMR (CD2Cl2
1H-NMR (CDCl3 298 K): l 1.49 (C–(CH3 3
6
) : s, 9H);
–S:
193 K): l(ppm)1.36 (D1,C–(CH3 3
6
) : s); 1.29 (D2,C–
(CH6 3)3: s); 4.39, (D1+D2, CH6 2–S (two mixed AB
3.10 (olefin protons: br. AB system, 2H); 4.21 (CH2
6
s, 2H); 7.35 (H(5pyr): m,1H); 7.51 (H(3pyr): d, J=7.5, 1H);
7.84 (H4(pyr): t, J=7.5,1H); 8.90 (H(6pyr): d, J=6.0,1H).
Complex 2g was prepared as 2d.
systems): m); 7.44 (D1+D2, H5(pyr): m); 7.77 (D1+D2,
H3(pyr): d, J=7.8); 8.00 (D1+D2,H(4pyr): t, J=7.8); 8.73
(D1+D2,H6(pyr): d, J=5.2); allyl signals: see Table 2.
5.3.2. [Pd(p2-(CHCN)2)(C5H3N-6-Me-2-CH2SC6H5)]
(2g)
5.2.6. [Pd(p3-1,1-Me2C3H3)(C5H4N-2-CH2SC(CH3)3)]
ClO4 (1f)
Yield 82% (pale yellow microcristals). Found: C
51.13; H 3.84; N 10.43; S 8.12. C17H15N3SPd requires C
51.07; H 3.78; N 10.51; S 8.02%. IR: w(CN) 2200 (fn):
Yield 97% (white microcrystals). Found: C 39.75; H
5.35; N 3.15; S 7.09. C15H24NSO4ClPd requires C
39.48; H 5.30; N 3.07; S 7.03%. IR: w(CN) 1603; w(ClO)
1
w(CN) 1602 (pyridine ring) cm−1 (KBr pellet). H-NMR
1
1090; l(ClO) 623 cm−1 (KBr pellet). H‘-NMR (CD2Cl2
(CDCl3 298 K): l(ppm) 2.93 (–CH6 3: s, 3H); 3.18 (olefin
298 K): l(ppm) 1.38 (D1,C–(CH3 3
6 ) : s), 1.32 (D2, C–
proton: bs, 2H); 4.51 (CH6 2 +
–S: s, 2H); 7.40 (H(3pyr)
(CH3)3: s); 1.47 (D1, CH3anti: s), 1.49 (D2,CH3anti: s);
6
H(5pyr)+H(phen): m, 7H); 7.67 (H(4pyr): t, J=7.7, 1H).
Complex 2a was prepared as in Ref. [2].
1.86 (D1, CH3syn: s); 1.83 (D2, CH3syn: s); 3.82 (D1,
Hanti: d, J=13.6), 3.22 (D2, Hanti: d, J=2.7); 4.10 (D1,
H
syn: d, J=7.5), 4.30 (D2, Hsyn: d, J=7.9); 4.40,
5.3.3. [Pd(p2-(CHCN)2(C5H4N-2-CH2SC6H5)) (2a)
(D1+D2, CH2–S (two mixed AB systems): m); 5.41
6
Yield 78% (pale yellow microcrystals). Found: C
49.99; H 3.41; N 10.86; S 8.16. C16H13N3SPd requires C
49.82; H 3.40; N 10.89; S 8.31%. IR: w(CN) 2199 (fn):
(D1, H2(allyl): d,d, J=13.6,7.5), 5.64 (D2 H(2allyl): d,d,
J=12.7,7.9); 7.58 (D1,H5(pyr): d,d, J=7.9, 5.3),7.45
(D2,H5(pyr): d,d, J=7.9, 4.8); 7.82 (D1, H3(pyr): d, J=7.9);
7.75 (D2, H3(pyr): d, J=7.9); 8.05 (D1,H4(pyr): t, J=7.9);
7.99 (D2,H4(pyr): t, J=7.9); 8.45 (D1, H6(pyr): d, J=5.3);
8.74 (D2, H6(pyr): d, J=4.8).
1
w(CN) 1601 (pyridine ring) cm−1 (Nujol mull). H-NMR
(CDCl3 298 K): l(ppm) 3.21 (olefin proton: bs, 2H); 4.48
(CH6 2 :
–S: bs, 2H); 7.51 (H3(pyr)+H5(pyr)+H(6pyr)+H(phen)
m, 7H); 7.82 (H4(pyr): t, J=7.7, 1H); 8.95 (H(6pyr): d,
J=5.0,1H).
5.2.7. [Pd(p3-C3H5)(C5H3N-6-Me-2-CH2 SC6H5)]ClO4
(1g)
5.4. Spectrophotomeric studies
Yield 92% (white microcrystals). Found: C 41.71; H
4.01; N 3.08; S 6.98. C16H18NSO4ClPd requires C
41.57; H 3.92; N 3.03; S 6.94%. IR: w(CN) 1603; w(ClO)
The kinetics of allyl amination of complexes 1 were
studied by adding known aliquots of amine solution to
a solution of 1, fn and the appropriate ligand N–SR in
the thermostatted cell compartment of the spectropho-
tometer. The reactants were such to ensure constant
excess over the metal complex ([Pd]0 ca. 1×10−4 mol
dm−3). The progress of the reaction was monitored by
1
1086; l(ClO) 625 cm−1 (KBr pellet). H-NMR (CD2Cl2
193 K): l(ppm) 2.76 (D1, –CH6 3: s), 2.72 (D2, –CH6 3: s);
4.73, (D1+D2, CH6 2–S (two mixed AB systems): m);
7.45 (D1+D2, H(phen)+H5(pyr)+H(3pyr): m); 7.77 (D1+
D2, H4(pyr): t, J=7.4); allyl signals: see Table 2.