Electronic Supplementary Information

Organophosphorus ligands with XPNSO skeleton (X = O, S) and their Pd(II) complexes.

Crystal and molecular structure of [{XP(OEt)2}(O2SR)]NH (X = O, R = Me, Ph; X = S, R =
C6H4Cl-4) and Pd[{SP(OEt)2}(O2SC6H4Cl-4)N]2

Dorel Oltean, Alpar Pöllnitz and Anca Silvestru*

Figure S1. Coupling scheme (a), experimental resonance (b), simulated resonance (c) and
theoretical interpretation (d) for the ABXY3 system in the 1H NMR spectrum of [{OP(OEt)2}
(O2SPh)]NH (2).
Figure S2. Coupling scheme (a), experimental resonance (b), simulated resonance (c) and
theoretical interpretation (d) for the ABXY3 system in the 1H NMR spectrum of [{OP(OEt)2}
(O2SC6H4CH3-4)]NH (3).
Figure S3. Coupling scheme (a), experimental resonance (b), simulated resonance (c) and
theoretical interpretation (d) for the ABXY3 system in the 1H NMR spectrum of [{SP(OEt)2}
(O2SC6H4Cl-4)]NH (4).
Figure S4. Coupling scheme (a), experimental resonance (b), simulated resonance (c) and
theoretical interpretation (d) for the ABXY3 system in the 1H NMR spectrum of
Pd[{SP(OEt)2}(O2SC6H4Cl-4)N]2 (12).
Table S1. Parameters used for the simulation of the 1H NMR resonances of the diastereotopic
PO-CH2-CH3 protons in compounds 2 – 4 and 12.

Line
Spin system, ppm Coupling
Cpd. Frequency width (Hz)
(equivalent spins) constants (Hz)
(A, B / Y)
JAB 10.0
A (1) 3.967
JAX 7.9
B (1) 4.088
2 300 MHz JBX 7.6 3.4 / 3.5
X (1) (31P)
JAY 6.9
Y (3) 1.224
JBY 6.9
JAB 10.0
A (1) 4.000
JAX 7.6
B (1) 4.115
3 300 MHz JBX 7.4 1.8 / 1.2
X (1) (31P)
JAY 7.1
Y (3) 1.261
JBY 7.1
JAB 9.8
A (1) 4.035 JAX 9.3
B (1) 4.140 JBX 9.2
4 300 MHz 0.8 / 0.6
X (1) (31P) JAY 6.9
Y (3) 1.266 JBY 7.05
JXY 0.8
JAB 9.6
A (1) 4.144
JAX 8.2
B (1) 4.270
12 300 MHz JBX 8.4 2.9 / 3
X (1) (31P)
JAY 7.0
Y (3) 1.364
JBY 7.0
Figure S5. Supramolecular associations in [{OP(OEt)2}(O2SMe)]NH (1).
H(1N)∙∙∙O(3’)a 1.94 Å; O(2)∙∙∙H(1A”)b 2.41 Å [ΣvdW(HO) 2.60 Å]
a
Symmetry equivalent position given by “prime” 0.5-x, -0.5+y, z; b Symmetry equivalent position given by
“second” -0.5+x, 1.5-y, -z;