348 Safin et al.
(m, overlapped with the solvent signal, Ph + NH)
(7.4) [(PPh4)2L2 + L]−. Calcd. for C40H46N2O2P2S2
(712.88): C, 67.39; H, 6.50; N, 3.93. Found: C, 67.48;
H, 6.57; N, 3.87.
1
ppm. 31P{ H} NMR: δ = 23.0 (1P, PPh4), 64.5 (1P,
NPS) ppm. IR: ν = 611 (P S), 1007 (POC), 1541
(SCN), 3285 (NH) cm−1. ES MS (positive ion): m/z
(%) = 339.2 (100) [PPh4]+, 671.4 (48.2) [PPh4L + H]+,
703.9 (21.6) [PPh4L + CH3OH + H]+, 1010.2 (74.6)
[PPh4L + PPh4]+, 1028.5 (11.7) [PPh4L + H2O +
PPh4]+, 1341.4 (17.3) [(PPh4)2L2 + H]+. ES MS (neg-
ative ion): m/z (%) = 330.7 (83.7) [L]−, 1000.3 (100)
[PPh4L + L]−, 1671.4 (11.3) [(PPh4)2L2 + L]−. Calcd.
for C37H40N2O2P2S2 (670.80): C, 66.25; H, 6.01; N,
4.18. Found: C, 66.17; H, 5.96; N, 4.22.
(PPh4)2LVI. Yield: 0.543 g (86%). 1H NMR:
δ = 1.23–1.36 (m, 24H, CH3, i-Pr), 4.78 (d sept,
3
3 JPOCH = 10.1 Hz, JH,H = 6.2 Hz, 4H, OCH),
6.95–7.91 (m, overlapped with the solvent signal,
1
Ph + C6H4 + NH) ppm. 31P{ H} NMR: δ = 24.1
(2P, PPh4), 62.7 (2P, NPS) ppm. IR: ν = 603
(P S), 1000 (POC), 1520 (SCN), 3258 (NH) cm−1.
ES MS (positive ion): m/z (%) = 339.4 (53.2)
[PPh4]+, 348.5 (100) [H2L-(i-PrO)2P(S)NCS + H]+,
379.2 (24.7) [H2L-(i-PrO)2P(S)NCS + CH3OH +
H]+, 685.3 (18.1) [PPh4HL- (i-PrO)2P(S)NCS + H]+,
958.5 (7.3) [PPh4HL + CH3OH + H]+, 1262.6 (62.7)
[(PPh4)2L + H]+, 1636.4 (5.9) [(PPh4)2L + 2H2O +
PPh4LIII. Yield: 0.562 g (82%). 1H NMR: δ = 1.37
(d, 3 JH,H = 6.2 Hz, 12H, CH3, i-Pr), 2.28 (s, 3H, CH3),
3
3
4.76 (d sept, JPOCH = 10.4 Hz, JH,H = 6.1 Hz, 2H,
OCH), 6.82–7.91 (m, overlapped with the solvent sig-
nal, Ph + C6H4 + NH) ppm. 31P{ H} NMR: δ = 23.6
PPh4]+. ES MS (negative ion): m/z (%)
=
1
(1P, PPh4), 64.2 (1P, NPS) ppm. IR: ν = 615 (P S),
1012 (POC), 1553 (SCN), 3298 (NH) cm−1. ES MS
(positive ion): m/z (%) = 339.6 (100) [PPh4]+, 702.6
(32.6) [PPh4L + H2O + H]+, 718.1 (12.9) [PPh4L +
CH3OH + H]+, 1040.7 (43.5) [PPh4L + H2O + PPh4]+,
1401.7 (9.2) [(PPh4)2L2 + CH3OH + H]+. ES MS
(negative ion): m/z (%) = 345.4 (100) [L]−, 1714.1
(9.7) [(PPh4)2L2 + L]−. Calcd. for C38H42N2O2P2S2
(684.83): C, 66.65; H, 6.18; N, 4.09. Found: C, 66.74;
H, 6.11; N, 4.03.
346.7 (27.3) [H2L-(i-PrO)2P(S)NCS-H]−, 633.9 (81.4)
[HL + CH3OH + H2O]−, 925.4 (100) [PPh4L]−,
957.0 (48.1) [PPh4L
+
CH3OH]−. Calcd. for
C68H74N4O4P4S4 (1263.50): C, 64.64; H, 5.90; N, 4.43.
Found: C, 64.50; H, 5.96; N, 4.39.
(PPh4)2LVII. Yield: 0.553 g (91%). 1H NMR:
3
δ = 1.19 (t, JH,H = 6.1 Hz, 24H, CH3, i-Pr), 3.92
3
(br s, 4H, CH2), 4.72 (d sept, JPOCH = 10.0 Hz,
3 JH,H = 6.2 Hz, 4H, OCH), 7.14–8.17 (m, overlapped
with the solvent signal, Ph + NH) ppm. 31P{ H}
1
PPh4LIV. Yield: 0.622 g (89%). 1H NMR: δ = 1.39
NMR: δ = 23.9 (2P, PPh4), 63.1 (2P, NPS) ppm.
IR: ν = 598 (P S), 996 (POC), 1564 (SCN), 3225
(NH) cm−1. ES MS (positive ion): m/z (%) = 331.4
(100) [H2L-(i-PrO)2P(S)NCS + CH3OH + H]+, 337.2
(37.2) [H2L- (i-PrO)2P(S)NCS + 2H2O + H]+, 339.1
(93.8) [PPh4]+, 928.2 (19.6) [PPh4HL + CH3OH +
H2O + H]+, 1245.8 (57.4) [(PPh4)2L + CH3OH +
H]+. ES MS (negative ion): m/z (%) = 316.4 (100)
[H2L-(i-PrO)2P(S)NCS −H + H2O]−, 536.6 (62.3)
[HL]−, 905.8 (72.8) [PPh4L + CH3OH]−. Calcd. for
C64H74N4O4P4S4 (1215.45): C, 63.24; H, 6.14; N, 4.61.
Found: C, 63.37; H, 6.08; N, 4.68.
3
3
(d, JH,H = 6.0 Hz, 6H, CH3, i-Pr), 1.42 (d, JH,H
=
6.1 Hz, 6H, CH3, i-Pr), 2.35 (s, 6H, CH3), 4.81 (d sept,
3 JPOCH = 10.6 Hz, 3 JH,H = 6.2 Hz, 2H, OCH), 7.03–8.07
(m, overlapped with the solvent signal, Ph + C6H3 +
NH) ppm. 31P{ H} NMR: δ = 22.4 (1P, PPh4), 63.7
1
(1P, NPS) ppm. IR: ν = 610 (P S), 998 (POC), 1562
(SCN), 3308 (NH) cm−1. ES MS (positive ion): m/z
(%) = 339.2 (79.4) [PPh4]+, 730.7 (100) [PPh4L +
CH3OH + H]+, 1039.2 (50.4) [PPh4L + PPh4]+, 1398.3
(27.6) [(PPh4)2L2 + H]+. ES MS (negative ion): m/z
(%) = 358.7 (92.7) [L]−, 1773.9 (16.1) [(PPh4)2L2 +
H2O + L]−. Calcd. for C39H44N2O2P2S2 (698.86): C,
67.03; H, 6.35; N, 4.01. Found: C, 67.11; H, 6.28; N,
3.97.
Physical Measurements
PPh4LV. Yield: 0.528 g (74%). 1H NMR: δ = 1.30
3
3
(d, JH,H = 6.2 Hz, 6H, CH3, i-Pr), 1.35 (d, JH,H
=
Infrared spectra were recorded with a Bruker
IFS66νS spectrometer in the range 400–3600 cm−1.
NMR spectra (CDCl3) were obtained on a Bruker
Avance 300 MHz spectrometer at 25◦C. 1H and
6.0 Hz, 6H, CH3, i-Pr), 2.32 (s, 9H, CH3), 4.70 (d
3
3
sept, JPOCH = 10.1 Hz, JH,H = 6.0 Hz, 2H, OCH),
7.12–8.27 (m, overlapped with the solvent signal,
Ph + C6H2 + NH) ppm. 31P{ H} NMR: δ = 22.7 (1P,
31P{ H} spectra were recorded at 299.948 and
1
1
PPh4), 63.9 (1P, NPS) ppm. IR: ν = 616 (P S), 1006
(POC), 1558 (SCN), 3321 (NH) cm−1. ES MS (posi-
tive ion): m/z (%) = 339.0 (62.4) [PPh4]+, 731.5 (32.7)
[PPh4L + H2O + H]+, 744.8 (100) [PPh4L + CH3OH +
H]+, 1460.2 (13.3) [(PPh4)2L2 + CH3OH + H]+.
ES MS (negative ion): m/z (%) = 370.2 (100) [L]−,
1137.0 (41.1) [PPh4L + CH3OH + H2O + L]−, 1798.4
121.420 MHz, respectively. Chemical shifts are re-
ported with reference to SiMe4 (1H) and 85% H3PO4
1
(31P{ H}). Electrospray ionization mass spectra were
measured with a Finnigan-Mat TCQ 700 mass spec-
trometer on a 10−6 M solution in CH3OH. The speed
of sample submission was 2 μL/min. The ioniza-
tion energy was 4.5 kV. The capillary temperature
Heteroatom Chemistry DOI 10.1002/hc