mp 147–148 ЊC (decomp.). IR spectrum in KBr, selected bands,
cmϪ1: 3460 mw ν(N–H), 3306 mw ν(N–H), 3206 mw ν(N–H),
1655 s ν(C᎐N), 1595 s ν(C᎐C), 1172 s ν(C–O), 704 mw δ(C–H).
(CHortho and meta), 131.5 (CHpara), 118.7 (Cipso), 144.9 (C᎐N), 160.8
᎐
(C᎐NNH ), and 168.1 (C᎐NH). The NMR data after ca. 20 h
᎐
᎐
2
[1H NMR (CDCl3), δ 1.31 (t, 7.6 Hz, 3H, CH2CH3), 1.99 (s, 3H,
᎐
᎐
TLC (eluent chloroform–acetone = 15 : 1), Rf = 0.54. 1H NMR
in CDCl3, δ 1.37 (t, J 7.5 Hz, 3H, CH3CH2), 3.09 (q, J 7.5 Hz,
CH3CH2), 2.31 (s, 3H), 6.01 (s, 2H, NH2), 7.17–7.52 (m, 6H, Ph
ϩ NH), NH is overlapped with the signals from the Ph group).
13C{1H} NMR in CDCl3, δ 10.2 and 26.8 (Et), 11.6 (Me), 128.6
CH C᎐N), 2.36 (q, 7.6 Hz, 2H, CH CH ), 5.52 (s, 2H, NH ),
᎐
3
2
3
2
7.13–7.46 (m, 5H, Ph). 13C{1H} NMR (CDCl ), δ 9.35 (CH C᎐
᎐
3
3
N), 10.41 (CH2CH3), 11.20 (CH2CH3), 120.62 (CH3CH2CN),
127.34–132.0 (m, Carom), 146.94 (C᎐NNH ), 161.97 (C᎐NO)].
᎐
᎐
2
The latter NMR data show that the liberated imine ligand
decomposes to give the parent nitrile and the hydrazone oxime.
In addition, the free hydrazone oxime was isolated as a solid
after slow evaporation of CDCl3. Complex [Pt(dppe)2]Cl2:
Anal. Calc. for C52H48Cl2P4Pt: C, 58.76; H, 4.52%. Found: C,
and 129.5 (CHortho
meta), 131.8 (CHpara), 119.8 (Cipso), 142.7
and
(C᎐NNH ), 164.0 (C᎐NO) and 173.1 (C᎐NH). 195Pt NMR
᎐
᎐
᎐
2
spectrum in CDCl3, δ Ϫ2023 (505 Hz).
58.69; H, 4.48%. IR spectrum in KBr, selected bands, cmϪ1
:
trans-[PtCl {NH᎐C(Et)ON᎐C(Me)C(Ph)᎐NN᎐CH(C H -2-
᎐
᎐
᎐
᎐
2
6
3
1482 mw ν(P–CPh), 1437 s ν(P–CH2), 697 and 702s δ(C–HPh). 1H
NMR (CDCl3), δ 3.39 (t, J 6.9 Hz, 4H, CH2), 7.30–7.70 (m,
20H, Ph). 31P{1H} NMR (CDCl3, rel. H3PO4), δ 47.9 (2368 Hz)
[lit.35 31P NMR spectrum in CDCl3, δ 47.0 (2360 Hz)].
OH-5-NO2}2] (5). 5-Nitrosalicylaldehyde (10 mg, 0.06 mmol)
was added to a solution of 4 (22 mg, 0.03 mmol) in CH2Cl2
(3 mL) at 45 ЊC and the reaction mixture was left to stand for
7 h, whereupon the solvent was evaporated in a flow of N2 to
dryness, the obtained solid was washed with three 5-mL
portions of Et2O and dried in vacuo at room temperature. Yield:
59%. Anal. Calc. for C38H38N10Cl2O8Pt: C, 44.36; H, 3.72; N,
13.62%. Found: C, 44.44; H, 3.63; N. 13.54%. FABϩ-MS, m/z:
752 [M Ϫ 2C6H3NO3H]ϩ, 682 [M Ϫ 2Cl Ϫ 2C6H3NO3H]ϩ, 647
[M Ϫ L]ϩ, 611 [M Ϫ Cl Ϫ L Ϫ H]ϩ, 576 [M Ϫ 2Cl Ϫ L]ϩ, where
The synthesis of heteronuclear complexes
A solution of 5 (20 mg, 0.0195 mmol) in CH2Cl2 (2 mL) was
added to a solution of M(OAc)2ؒnH2O [M = Cu, n = 2; M = Co,
n = 4] (0.0195 mmol) in CH3OH (3 mL). The brown precipitate
which formed immediately was isolated by filtration, washed
three times with hot methanol and dichloromethane and dried
in vacuo.
Yield: 74%. Anal. Calc. for C38H38N10Cl2O8CuPtؒCH2Cl2: C,
39.79; H, 3.42; N, 11.89%. Found: C, 39.54; H, 3.11; N, 11.61%.
The compound is stable on heating at least up to 250 ЊC. IR
spectrum in KBr, selected bands, cmϪ1: 3290 mw ν(N–H), 1660
L
is NH᎐C(Et)ON᎐C(Me)C(Ph)᎐NN᎐CH(C H -2-OH-5-
᎐ ᎐ ᎐ ᎐
6 3
NO2); mp 164 ЊC (decomp.). IR spectrum in KBr, selected
bands, cmϪ1: 3287 mw ν(N–H), 1658 and 1612 s ν(C᎐N), 1595 s
᎐
ν(C᎐C), 1522 mw ν (NO ), 1340 s ν (NO ), 1159 s ν(C–O), 706
᎐
as
2
s
2
mw δ(C–H). TLC (eluent chloroform–acetone = 10 : 1), Rf =
0.61. 1H NMR in CDCl3, δ 1.39 (t, J 7.5 Hz, 3H, CH3CH2), 3.12
(q, J 7.5 Hz, 2H, CH3CH2), 2.47 (s, 3H, Ph), 6.97–8.29 (m, 8H,
s ν(C᎐N), 1604 s ν(C᎐N), 1546 mw ν (NO ), 1316 s ν (NO ).
᎐
᎐
as
2
s
2
Ph), 7.54 (s, 1H, NH), 8.78 (s, 1H, HC᎐N), 11.72 (s, 1H, OH).
᎐
Yield: 56%. Anal. Calc. for C38H38N10Cl2O8CoPtؒCH2Cl2: C,
39.94; H, 3.44; N, 11.94% Found: C, 39.80; H, 3.03; N, 11.43%.
The compound is stable on heating at least up to 250 ЊC. IR
spectrum in KBr, selected bands, cmϪ1: 3287 mw ν(N–H), 1653
13C{1H} NMR in CDCl3, δ 10.9 and 27.4 (Et), 13.3 (Me), 117.6
and 118.9 (Cipso), 128.5–132.4 (m, Carom), 164.6 (C᎐N), 165.8
᎐
(C᎐N) and 173.6 (C᎐NH). 195Pt NMR spectrum in CDCl3, δ
᎐
᎐
Ϫ2041 (540 Hz).
s ν(C᎐N), 1605 s ν(C᎐N), 1545 mw ν (NO ), 1315 s ν (NO ).
᎐
᎐
as
2
s
2
trans-[PtCl {NH᎐C(Et)ON᎐C(Me)C(Ph)᎐NN᎐CH(C H -4-
᎐
᎐
᎐
᎐
2
6
4
X-Ray structure determinations
NO2}2] (6). 4-Nitrobenzaldehyde (9 mg, 0.06 mmol) was added
to a solution of 4 (22 mg, 0.03 mmol) in CH2Cl2 (3 mL) at 45 ЊC
and the reaction mixture was left to stand for 12 h, whereupon
the solvent was evaporated in a flow of N2 to dryness, the
obtained oily residue was left to stand for 10 h in methanol
(5 mL, 50 ЊC) until the yellow crystalline product formed. This
product was washed with three 3-mL portions of Et2O and
dried in vacuo at room temperature. Yield: 27%. Anal. Calc. for
C38H38N10Cl2O6Pt: C, 45.78; H, 3.82; N, 14.06%. Found: C,
45.69; H, 3.74; N. 13.94%. FABϩ-MS, m/z: 998 [M ϩ 2H]; mp
171–172 ЊC (decomp.). IR spectrum in KBr, selected bands,
cmϪ1: 3274 mw ν(N–H), 1661 and 1638 s ν(C᎐N), 1596 s ν(C᎐
The X-ray diffraction data were collected with a Nonius
KappaCCD diffractometer using Mo-Kα radiation (λ =
0.71073 Å). Single crystals of 3–5 were mounted in inert oil
within the cold gas stream of the diffractometer. The
Denzo-Scalepack36 program package was used for cell refine-
ments and data reduction. Structures were solved by direct
methods using the SHELXS-97 or SIR-97 programs.37,38
A
multiscan absorption correction based on equivalent reflections
(XPREP in SHELXTL v. 6.12)39 was applied to all data (T min
/
T max values were 0.24824/0.30984, 0.19314/0.26538, and
0.31969/0.37318, respectively, for 3–5). All structures were
refined with SHELXL-9740 and WinGX graphical user inter-
face.41 In 3 and 4, NH and NH2 were located from the difference
Fourier map and refined isotropically. In 5, the OH hydrogen
was also located from Fourier map but not refined. All other
hydrogens were placed in idealized positions and constrained
to ride on their parent atom. The crystallographic data are
summarized in Table 1. Selected bond lengths and angles
are shown in the figure captions.
᎐
᎐
C), 1521 s νas(NO2), 1344 s νs(NO2), 1161 mw ν(C–O), 691 mw
δ(C–H). TLC (eluent chloroform–acetone = 10 : 1), Rf = 0.64.
1H NMR in CDCl3, δ 1.47 (t, J 7.5 Hz, 3H, CH3CH2), 3.21 (q,
J 7.5 Hz, 2H, CH3CH2), 2.38 (s, 3H, Ph), 7.51–8.35 (m, 10H,
Ph), 8.64 s, 1H, HC᎐N), NH is overlapped with the signals of
᎐
the Ph group. 13C{1H} NMR in CDCl3, δ 10.2 and 27.0 (Et),
17.3 (Me), 118.4 and 119.9 (Cipso), 128.5–132.4 (m, Carom), 159.8
(C᎐N), 161.3 (HC᎐N), 163.4 (C᎐NH). 195Pt NMR spectrum in
᎐
᎐
᎐
CDCl3, δ Ϫ1561 (580 Hz).
CCDC reference numbers 231143–231145.
lographic data in CIF or other electronic format.
Liberation of the ligand from complex 4
Dppe (11 mg, 0.028 mmol) was added at room temperature to a
solution of 4 (10 mg, 0.014 mmol) in chloroform (2 mL). A
colorless crystalline precipitate of [Pt(dppe)2]Cl2 was removed
by filtration after 30 min (14.2 mg, 98%) and the free ligand was
characterized by NMR spectroscopy. 1H NMR in CDCl3, δ 1.20
(t, J 7.83, 3H, CH3CH2), 3.51 (q, J 7.08, 2H, CH3CH2), 2.30
(s, 3H, Me), 5.85 (s, 2H, NH2), 7.22–7.52 (m, 6H, Ph), NH
is overlapped with the signals of the Ph group. 13C{1H} NMR
in CDCl3, δ 9.4 and 26.5 (Et), 10.4 (Me), 127.3 and 128.1
Acknowledgements
D. A. G. expresses gratitude to the Foundation for Science and
Technology (FCT) and the POCTI program (FEDER funded),
Portugal (grant SFRH/BPD/11685/2002) for the fellowship.
M. H. would like to thank the Academy of Finland for financial
support. A. J. L. P. and V. Yu. K. are grateful to the FCT
and the POCTI program (POCTI/QUI/43415/2001 project)
D a l t o n T r a n s . , 2 0 0 4 , 1 0 9 7 – 1 1 0 3
1101