NMR spectrum of a freshly prepared CDCl
3
solution of the crystals showed a signal at 5.60 ppm
P-Pt = 3860 Hz). The P-NMR spectrum of another sample of the crystals dissolved in 1,2-DCE
showed after 2h four signals: 5.29 (69%), 2.46 (27%), 1.33 (4%), 7.37 (traces). The isomer
1
31
(
J
3
1
responsible of the P-NMR signal at 2.46 ppm was crystallized and identified (single crystal X-ray
diffraction) as (E)-trans-[ PtCl (PPh )(1)] {(E)-trans-4}. A second crop of product was precipitated
2
3
as a mixture of isomers (total isolated yield 51%). We report the spectroscopic characterization for
the species (Z)-cis-4 and (E)-trans-4.
(
Z)-cis-4. C27
H
28Cl
2
NO
~
4
PPt Anal. Calc.: C 44.6, H 3.9, N 1.9 %; Exp.: C 44.8, H 4.4, N 2.0. FTIR
-1
~
~
~
1
4
(
ATR, cm ): 3159 (υ OH), 3048 (υ CH), 2992 (υ CH), 1623 (υ CN). H-NMR: 8.66 (d, 1H, JH-P=4
Hz, CHN); 8.32 (bs, 1H, OH); 7.78 (s, 1H, Harom); 6.86 (d, 1H, J=8.9 Hz, Harom); 7.53-7.45 (m, 10H, Harom
+
31
1
H
arom PPh
3
); 7.36-7.32 (m, 6H, Harom PPh
3
3 3
) 4.05 (s, 3H, OCH ); 3.98 (s, 3H, OCH' ). P-NMR: 5.60 ( JP-
Pt=3860 Hz).
1
4
(
E)-trans-4. H-NMR: 10.9 (s, 1H, OH); 8.45 (d, JH-P=3 Hz, CHN); 7.82-7.78 (m, 6H, Harom PPh
3
); 7.73 (s,
1
H, Harom); 7.59 (d, 1H, J= 8.6 Hz, Harom); 7.58-7.46 (m, 9H, H arom PPh
3
); 6.94 (d, J=8.6 Hz, Harom); 3.97 (s,
31
1
3
H, OCH
3
); 3.92 (s, 3H, OCH'
3
). P-NMR: 2.54 ( JP-Pt=3658 Hz).
2
.2.2. [PtCl
2
(PPh ){N(OH)=CH(1-Naphtyl)}] ([PtCl (PPh )(2)], 5)
3 2 3
A sample (0.194 g) of trans-[Pt(µ-Cl)Cl(PPh
3
)]
2
[4h] (0.36 mmol of Pt) was suspended in 1,2-DCE
(
15.0 mL) and treated with a solution of aldoxime 2 (0.064 g) in the same solvent (2/Pt molar ratio=
1.0). The suspension was refluxed (84 °C) 24h. The initially orange suspension turned into a yellow
solution and a colorless solid formed. The solid was filtered and dried under vacuum (0.061 g) and
identified as (Z)-cis-5. The liquid phase was refluxed (12h) and treated with heptane. A second crop
of solid was obtained and identified as (E)-trans-5. The total, isolated yield was 60%. We report the
spectroscopic characterization for the species (E)-trans- and (Z)-cis-5.
(
2
Z)-cis-5. C29H24Cl NOPPt. Anal. Calc.: C 49.8, H 3.5, N 2.0 %; Exp.: C 49.4, H 4.0, N 2.0%.
-1
~
~
~
~
1
FTIR (ATR, cm ): 3117 (υ OH), 3049 (υ CH), 3006 (υ CH), 1618 (υ CN). H-NMR: 9.85 (d, 1H,
J=7 Hz, Harom); 8.81 (s, 1H, OH); 8.78 (d, 1H, CHN); 8.08 (d, 1H, J=8.4 Hz, Harom); 7.88 (d, 1H, J=8.3 Hz,
Harom); 7.78 (dd, 1H, J=J'= 7.7 Hz, Harom); 7.52 (dd, 1H, J=J'= 7.3 Hz, Harom); 7.38-7.30 (m, 10H, Harom +
3
1
1
H
arom PPh
3
3
); 7.21-7.18 (m, 6H, Harom PPh ), 6.89 (d, 1H, J=8.2Hz, Harom). P-NMR: 5.60 ( JP-Pt=3860 Hz).
1
(
E)-trans-5. H-NMR: 11.05 (d, 1H, J=3.4 Hz, OH); 9.46 (d, 1H, J= 2.5 Hz, CHN); 8.40 (d, 1H, J=7.3 Hz,
Harom); 8.14 (d, 1H, J=8.1 Hz, Harom); 8.00 (d, 1H, J=8.1 Hz, Harom); 7.90 (d, 1H, J=7.3 Hz, Harom); 7.86-7.82
1
3
(
3 3
m, 6Hz, Harom PPh ); 7.60-7.45 (m, 12H, Harom+ Harom PPh ). C-NMR: 148.7, 134.8 (d, JC-P= 10.5 Hz),