5364 Organometallics, Vol. 25, No. 22, 2006
CanoVese et al.
(C2′py); quinoline carbons, δ 122.97 (C3qui), 125.81 (C6qui), 130.08
(C5qui), 133.15 (C8aqui), 134.63 (C8qui), 136.92 (C4qui), 145.58 (C4aqui),
153.45 (C2qui); phenyl carbons, δ 128.78 (Ccph), 129.56 (Cbph),
129.81 (Caph), 144.47 (Cdph); naphthoquinone carbons, δ 124.50,
124.62, 130.83, 130.95, 136.70; carbonyl carbons, δ 178.94, 180.06
(CdO). Anal. Calcd for C32H25N3O4PdS: C, 58.76; H, 3.85; N,
6.42. Found: C, 58.66; H, 3.81; N, 6.38.
The following complexes were synthesized in an analogous way
using the appropriate ligands.
[PdC4(COOMe)4(NSN(Qui))]. Yield: 75% (yellow micro-
crystals). IR (KBr pellet): νC-H 3078.6, 2999.6, 2953.6, 2841.7,
1
νCdO 1709.7, νCdN 1604.4 cm-1. H NMR (CD2Cl2, T ) 298 K,
ppm): methyl ester protons, δ 3.11, 3.63 (s, 12H, -COOCH3);
thiomethyl protons, δ 4.53 (s, 2H, pyr CH2S), pyridine protons, δ
[Pd(η2-Nq)(NNNtos(Py)]. Yield: 91% (red microcrystals). IR
(KBr pellet): νC-H 3072.0, 3026.0, 2927.2, νCdO 1624.1, 1584.6
7.05 (t, 1H, H5′py, J5′-6′ ) 6.59 Hz), 7.13 (d, 1H, H3′py, J3′-4′
)
6.59 Hz), 7.50 (td, 1H, H4′py, J4′-5′ ) 6.59 Hz, J4′-6′ ) 1.50 Hz),
8.70 (d, 1H, H6′py, J6′-5′ ) 6.59 Hz); quinoline protons, δ 7.55 (dd,
1H, H3qui, J3-2 ) 4.81 Hz), 7.63 (t, 1H, H6qui, J6-7 ) 7.80 Hz),
1
cm-1. H NMR (CD2Cl2, T ) 298 K, ppm): methyl protons, δ
2.53 (bs, 3H, -CH3); olefin protons, δ 4.60 (bs, 2H, CdCHnaphtho);
aminomethyl protons, δ 4.73 (bs, 4H, pyr- CH2N); pyridine protons,
7.92 (d, 1H, H5qui, J5-7 ) 1.23 Hz), 8.29 (dd, 1H, H4qui, J4-3
8.34 Hz), 8.37 (dd, 1H, H7qui, J5-6 ) 7.80 Hz), 9.43 (dd, 1H, H2
)
δ 7.18 (t, 2H, H5pyr, J5-6 ) 6.12 Hz), 7.52, 7.50 (m, 4H, H3
,
pyr
,
qui
HArnaphtho), 7.65 (td, 2H, H4pyr, J4-3 ) J4-5 ) 7.72 Hz, J4-6 ) 1.51
Hz), 8.24 (bs, 2H, H6pyr); phenyl protons, δ 7.43, 7.65 (AB system,
4H, Hc, Hb); aromatic naphthoquinone protons, δ 8.02 (bs, 2H,
HArnaphtho). 1H NMR (CDCl3, T ) 223 K, ppm): methyl protons, δ
2.52 (s, 3H, -CH3, M), 2.64 (s, 3H, -CH3, m); aminomethyl
protons, δ 4.86, 4.94 (AB system, 4H, pyr CH2N, J ) 14.9 Hz,
M), 4.03, 4.64 (AB system, 4H, pyr CH2N, J ) 14.8 Hz, m); olefin
J2-4 ) 1.46 Hz). 13C NMR (CD2Cl2, T ) 298 K, ppm): thiomethyl
carbon, δ 45.80 (pyr CH2S), methyl carbons, δ 50.09, 50.88
(-COOCH3); pyridine carbons, δ 122.93 (C5′py), 124.99 (C3′py),
137.57 (C4′py), 151.96 (C6′py), 156.75 (C2′py); quinoline carbons, δ
122.08 (C3qui), 127.53 (C6qui), 129.60 (C4aqui), 129.75 (C8qui), 131.20
(C5qui), 138.82 (C4qui), 140.97 (C7qui), 147.46 (C8aqui), 154.89 (C2qui);
carbonyl carbons, δ 164.01, 173.29 (-COOCH3); cyclobutadienyl
carbons, δ 141.06, 165.72 (CRdC, CâdC). Anal. Calcd for
C27H24N2O8PdS: C, 50.44; H, 3.76; N, 4.36. Found: C, 50.41; H,
3.69; N, 4.31.
protons, δ 4.64 (s, 2H, CdCHnaphtho, M), 4.65 (s, 2H, CdCHnaphtho
,
m); pyridine protons, δ 7.99 (d, 2H, H6pyr, J6-5 ) 5.1 Hz, M), 8.60
(d, 2H, H6pyr, J6-5 ) 5 Hz, m); aromatic system, δ 7-8.25. Anal.
Calcd for C29H25N3O4PdS: C, 56.36; H, 4.08; N, 6.80. Found: C,
56.40; H, 4.02; N, 6.78.
[PdC4(COOMe)4(NNNtos(Py))]. Yield: 98% (yellow micro-
crystals). IR (KBr pellet): νC-H 2993.1, 2953.6, 2841.7,
[Pd(η2-Nq)(MeNSt-Bu)]. Yield: 94% (red microcrystals). IR
(KBr pellet): νC-H 3006.2, 2953.6, 2841.7, νCdO 1624.1, 1584.6
1
νCdO 1716.3, νCdN 1611.0 cm-1. H NMR (CD2Cl2, T ) 298 K,
ppm): methyl protons, δ 2.52 (s, 3H, -CH3); methyl ester protons,
δ 3.07, 3.62 (s, 12H, -COOCH3); aminomethyl protons, δ 5.05,
5.35 (AB system, 2H, pyr CH2N); pyridine protons, δ 7.30 (ddd,
1
cm-1, νCdN 1604.4 cm-1. H NMR (CDCl3, T ) 298 K, ppm):
tert-butyl protons, δ 1.31 (s, 9H, -(CH3)3); methyl protons, δ 2.80
(s, 3H, -CH3); thiomethyl protons, δ 4.06 (s, 2H, pyr CH2S);
olefinic protons, δ 4.81 (AB system, HCdCHnaphtho); pyridine
protons, δ 7.17 (m, 2H, H3py, H5py), 7.58 (t, 1H, H4py, J ) 7.63
1H, H5py, J5-4 ) 6.37 Hz, J5-3 ) 2.26 Hz), 7.75 (m, 2H, H3
,
py
H4py), 8.61 (d, 1H, H6py, J6-5 ) 5.34 Hz); phenyl protons, δ 7.45,
7.83 (AB system, Hc, Hd, 4H). 13C NMR (CD2Cl2, T ) 298 K,
ppm): methyl carbon, δ 21.52 (-CH3); methyl ester carbons, δ
50.29, 51.18 (-COOCH3); aminomethyl carbon, δ 58.94 (pyr
CH2N); pyridine carbons, δ 124.23 (C5py), 126.8 (C3py), 138.74
(C4py), 150.04 (C6py), 158.15 (C2py); phenyl carbons, δ 126.8 (Cbph),
130.30 (Ccph), 135.66 (Cdph), 144.56 (Caph); carbonyl carbons, δ
143.01, 163.58, 163.70, 172.62 (-COOCH3). Anal. Calcd for
C31H31N3O10PdS: C, 50.04; H, 4.20; N, 5.65. Found: C, 50.08;
H, 4.23; N, 5.61.
Hz); naphthoquinone protons, δ 7.51, 8.03 (m, 4H, HArnaphtho). 13
C
NMR (CDCl3, T ) 298 K, ppm): methyl carbon, δ 28.15 (-CH3);
tert-butyl carbons, δ 30.07 (-C(CH3)3); thiomethyl carbons, δ 39.53
(pyr CH2S); quaternary tert-butyl carbons, δ 48.13 (-C(CH3)3);
olefin carbons, δ 58.55, 62.37 (CdCnaphtho); pyridine carbons, δ
119.83 (C3py), 123.39 (C5py), 128.86 (C6py), 137.76 (C4py), 143.21
(C2py); naphthoquinone carbons, δ 125.23, 131.25 (CArnaphtho), 135.84
(Cquatnaphtho), carbonyl carbons, δ 157.89, 162.17 (CdOnaphtho). Anal.
Calcd for C21H21NO2PdS: C, 54.84; H, 5.04; N, 3.05. Found: C,
54.88; H, 4.98; N, 3.11.
[PdC4(COOMe)4(NNNtos(Qui))]. Yield: 92% (yellow micro-
crystals). IR (KBr pellet): νC-H 3078.6, 2993.1, 2953.6, 2841.7,
1
νCdO 1709.7, νCdN 1604.4 cm-1. H NMR (CDCl3, T ) 298 K,
Synthesis of the Palladacyclopentadienyl Derivatives. The
synthesis of the complexes [PdC4(COOMe)4(SNS(Me))] and [PdC4-
(COOMe)4(SNS(Ph))] was carried out according to published
procedures.4
ppm): methyl protons, δ 2.41 (s, 3H, -CH3); methyl ester protons,
δ 2.89, 3.35, 3.63, 3.78 (s, 12H, -COOCH3); aminomethyl protons,
δ 4.64, 5.28 (AB system, 2H, pyr CH2N); pyridine protons, δ 6.97
(t, 1H, H5′py, J5′-6′ ) 6.22 Hz), 7.06 (d, 1H, H3′py, J3′-4′ ) 7.80
Hz), 7.46 (t, 1H, H4′py, J4′-5′ ) 6.97 Hz), 8.46 (d, 1H, H6′py); phenyl
protons, δ 7.45, 8.46 (AB system, Hc, Hb, 4H); quinoline protons,
[PdC4(COOMe)4(NSN(Py))]. To 0.0706 g (0.327 mmol) of the
ligand NSN(Py) dissolved in 12 mL of anhydrous acetone was
added 0.1065 g (0.273 mmol) of [PdC4(COOMe)4]n under an inert
atmosphere. The resulting solution was stirred for 2 h at room
temperature and concentrated under vacuum. Addition of diethyl
ether (20 mL) yields 0.1197 g (0.197 mmol) of the title substrate
as yellow microcrystals. The complex was filtered off, washed with
diethyl ether, and dried in a desiccator. Yield: 72%.
δ 7.52 (dd, 1H, H3qui, J3-2 ) 4.92 Hz), 7.62 (t, 1H, H6qui, J6-7
7.88 Hz), 7.83 (dd, 1H, H7qui, J7-5 ) 1.32 Hz), 8.21 (dd, 1H, H4
)
qui
,
J4-3 ) 8.39 Hz), 8.34 (dd, 1H, H5qui, J5-6 ) 7.88 Hz), 9.46 (dd,
1H, H2qui, J2-4 ) 1.6 Hz). 13C NMR (CDCl3, T ) 298 K, ppm):
methyl carbon, δ 21.56 (-CH3); aminomethyl carbon, δ 58.51 (pyr
CH2N); methyl carbons, δ 48.82, 50.69, 50.95, 51.21 (-COOCH3);
pyridine carbons, δ 123.38 (C5′py), 125.12 (C3′py), 138.09 (C4′py),
151.39 (C6′py), 154.84 (C2′py); quinoline carbons, δ 122.06 (C3qui),
127.17 (C6qui), 130.55 (C5qui), 131.41 (C7qui), 134.61 (C8qui), 138.74
(C4qui), 144.60 (C4aqui), 154.47 (C2qui); phenyl carbons, δ 129.85
(Ccph), 130.69 (Cbph), 131.69 (Caph), 145.85 (Cdph); cyclobutadienyl
carbons, δ 141.16, 143.55, 163.37, 167.43 (CdC); carbonyl carbons,
δ 163.54, 165.00, 172.75, 173.34 (-COOCH3). Anal. Calcd for
C34H31N3O8PdS: C, 52.35; H, 4.01; N, 5.39. Found: C, 52.31; H,
3.95; N, 5.33.
IR (KBr pellet): νC-H 2993.1, 2953.6, 2835.1, νCdO 1703.1,
1
νCdN 1611.0 cm-1. H NMR (CDCl3, T ) 298 K, ppm): methyl
ester protons, δ 3.07, 3.64 (s, 12H, -COOCH3); thiomethyl protons,
δ 4.18, 5.28 (AB system, 2H, pyr CH2S); pyridine protons, δ 7.21
(m, 1H, H3py, H5py), 7.66 (t, 1H, H4py, J4-5 ) J4-3 ) 7.63 Hz),
8.57 (m, 1H, H6py, J6-5 ) 5.47 Hz). 13C NMR (CDCl3, T ) 298 K,
ppm): thiomethyl carbon, δ 43.37 (pyr CH2S); methyl ester carbons,
δ 50.23 (-COOCRH3), 51.18 (-COOCâH3); pyridine carbons, δ
123.27 (C5py), 124.64 (C3py), 138.61 (C4py), 150.00 (C6py), 162.23
(C2py); cyclobutadienyl carbons, δ 163.81 (CdC), carbonyl carbons,
δ 163.88 (-CâOOCH3), 172.62 (-CROOCH3). Anal. Calcd for
C24H24N2O8PdS: C, 47.49; H, 3.99; N, 4.62. Found: C, 47.51; H,
4.03; N, 4.52.
X-ray Diffraction Analysis. For complexes 1 ([Pd(NNNtos-
(Qui))(η2-tmetc)]), 2 ([Pd(NNNtos(Py))(η2-tmetc)]), 3 ([Pd(NNNtos-
(Qui))(η2-Nq)]), and 4 ([Pd(NSN (Qui))(η2-tmetc)]), single crystals,