M.C. Risi et al.
Inorganica Chimica Acta 526 (2021) 120506
14. General procedure for the synthesis of platinum(II),
palladium(II), nickel(II) and gold(III)
(NCH2, d, 2H), 4.2 (C=CH2, m, 2H), 2.19 (Tol CH3, s, 3H).
[Au{TolSO2NC(S)NPh}(bp)] 2i. Deep yellow solid. Elemental anal-
ysis: Found (%) C 46.14; H 3.31; N 6.22. Calculated (%) C 46.63; H 3.31;
N 6.28. M.p. 121 ◦C. ESI MS: m/z [M + H]+ 670 and [M + Na]+ 692.
FTIR (cmꢀ 1): 1611(w), 1592(w), 1493(vs,br), 1447(m), 1336(s), 1281
14.1. Complexes of sulfonylthioureas
1
Equimolar amounts of the ligand and metal starting material were
suspended in MeOH (30 mL) with stirring. The mixture was brought to
reflux, followed by the addition of triethylamine (0.8 mL, excess). The
solution was refluxed for 10 min. followed by the addition of distilled
water (40 mL) to precipitate any solid. The mixture was cooled rapidly
using an ice bath to facilitate precipitation and coagulation. Where
stated in Table 3, solid NaCl (0.4 g) was added and allowed to stir for 1 h
to aid coagulation of the precipitate. The solid was filtered and washed
with hot water (2 × 20 mL, or 4 × 50 mL if NaCl added) and dried under
vacuum. Details pertaining to each compound are given in Table 3.
Elemental analytical data for complexes 2b and 2c were not obtained
due to the instability of these products and formation of trinuclear sul-
fido aggregates.
(w), 1145(s), 1185(m), 690(m), 545(m). NMR: H, δ 8.9–6.7 (m, aro-
matic), 3.41 (2H, s, CH2) and 2.40 (3H, s, CH3).
15. Formation of [Pd3(
μ
-S)2(dppe)3]2þ
The complex [Pd{p-TolSO2C(S)NPh}(dppe)] 2b (20 mg) was dis-
solved in methanol (20 mL) and heated slightly below boiling for 7 h.
Alternatively, the same complex (20 mg) was dissolved in chloroform
(0.5 mL), and allowed to stand at room temperature for 14 d. The so-
lution was analysed by positive ion ESI MS.
16. X-ray crystal structure determinations
[Pt{TolSO2NC(S)NPh}(PPh3)2] 2a Pale yellow solid. Elemental
analysis: Found (%) C 58.89; H 4.73; N 2.72. Calculated (%) C 58.65; H
4.14; N 2.74. M.p. 279 ◦C. ESI MS: m/z [M + H]+ 1025. FTIR (cmꢀ 1):
3204(w,br), 3047(w,br), 1600(s), 1563(vs), 1486(s), 1434(s), 1312(s),
1098(s), 754(s), 693(vs), 544(s). NMR: 31P{1H}, δ (ppm) 15.6 [d, 1JPtP
3039, 2JPP 21] and 10.7 [d, 1JPtP 3380, 2JPP 22]; 1H, δ 7.7–6.2 (m, ar-
omatic), 2.35 (3H, s, CH3).
Crystals of the thiourea 1b were grown by slow evporation of a
dichloromethane solution, at room temperature. Crystals of the com-
plexes 2a and 2f were obtained by slow diffusion of diethyl ether into a
dichloromethane solution at room temperature. Intensity data were
obtained on an Agilent SuperNova, Single source at offset, Atlas
diffractometer with graphite-monochromated Cu—Kα radiation and
corrected for absorption using a multi-scan procedure.[39] Using Olex2,
[40] the structures were solved with the Olex2.solve [41] structure so-
lution program using Charge Flipping and refined with the Olex2.refine
[41] refinement package using Gauss–Newton minimisation. Crystal
and refinement details are summarised in Table 4.
[Pd{TolSO2NC(S)NPh}(dppe)] 2b. Orange-brown solid. M.p. 129 ◦C.
ESI MS: m/z [M + H]+ 808. FTIR (cmꢀ 1): 1589(w), 1471(vs), 1446(s),
1325(s), 1276(w), 1140(s), 1103(m), 1089(s), 691(s), 530(m). NMR: 31
P
{1H}, δ (ppm) 56.9 (d, 2JPP 34) and 49.5 (d, 2JPP 35); 1H, δ 8.0–6.5 (m,
aromatic), 2.34 (3H, s, CH3).
[Pd{TolSO2NC(S)NPh}(bipy)] 2c. Orange-red solid. M.p. 143 ◦C. ESI
MS: m/z [M + H]+ 567 and [M + Na]+ 589. FTIR (cmꢀ 1): 1601(w), 1487
(s), 1446(m), 1330(m), 1276(w), 1208(vw), 1140(s), 1088(s), 766(w),
692(w). NMR: 1H, δ 8.4–6.8 (m, aromatic), 2.37 (3H, s, CH3).
[Pt{TolSO2NC(S)NPh}(dppp)] 2d. Off white solid. M.p. 147–150 ◦C.
ESI MS: m/z [M + H]+ 912 and [M + Na]+ 934. FTIR (cmꢀ 1): 1590(w),
1473(vs), 1364(s), 1328(s), 1277(m), 1140(s), 1102(m), 1089(m), 690
(s), 545(m), 514(s). NMR: 31P{1H}, δ (ppm) ꢀ 2.9 [d, 1JPtP 2906, 2JPP 33]
CRediT authorship contribution statement
Matthew C. Risi: Investigation, Formal analysis, Methodology,
Writing - original draft. Graham C. Saunders: Formal analysis, Inves-
tigation, Methodology, Supervision, Writing - original draft. William
Henderson: Conceptualization, Methodology, Project administration,
Resources, Supervision, Writing - original draft.
1
2
1
and ꢀ 11.2 [d, JPtP 3024, JPP 33]; H, δ 7.8–6.3 (m, aromatic), 2.35
(3H, s, CH3). The complex was only characterised spectroscopically, and
satisfactory microelemental analytical data could not be obtained.
[Ni{TolSO2NC(S)NPh}(dppe)] 2e. Orange solid. Elemental analysis:
Found (%) C 63.01; H 4.82; N 3.53. Calculated (%) C 63.09; H 4.77; N
3.68. M.p. 140–145 ◦C. ESI MS: m/z [M + H]+ 760.8. FTIR (cmꢀ 1): 1626
(w), 1591(w), 1484(vs), 1435(s), 1328(s), 1289(m), 1126(s), 1097(s),
693(s). NMR: 31P{1H}, δ (ppm) 58.4 (d, 2JPP 38) and 53.5 (d, 2JPP 38);
1H, δ 8.1–6.4 (m, aromatic), 2.34 (3H, s, CH3).
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We thank the University of Waikato for financial support of this
work, and Dr. Judith Burrows for technical assistance.
[Pt{CH3SO2NC(S)NPh}(PPh3)2] 2f. Pale yellow solid. Elemental
analysis: Found (%) C 55.72; H 3.54; N 2.77. Calculated (%) C 55.75; H
4.04; N 2.96. M.p. 260–266 ◦C. ESI MS: m/z [M + H]+ 948.08 (calcu-
Appendix A. Supplementary data
lated, 948.16), [M + Na]+ 970.00 (calculated, 970.14). FTIR (cmꢀ 1
)
1591(w), 1484 (vs), 1436(s), 1131(s), 1098(m), 694(s), 526(s). NMR:
31P{1H}, δ (ppm) 15.5 (d, 1JPtP 3059, 2JPP 22) and 10.4 (d, 1JPtP 3358,
2JPP 22). 1H, δ 7.7–6.2 (m, aromatic), 2.88 (3H, s, CH3).
Supplementary data to this article can be found online at https://doi.
[Pt{CH3CH2SO2NC(S)NPh}(PPh3)2] 2g. Pale yellow solid. M.p.
220–227 ◦C. ESI MS: m/z [M + H]+ 962.34 (calculated, 962.17). FTIR
(cmꢀ 1): 3053(w), 2922(w), 1631(w, br), 1591(m), 1484(vs), 1328(s),
1289(s), 1126(vs), 1097(s), 997(m), 693(vs, br), 547(s). NMR: 31P{1H},
δ (ppm) 15.6 (d, 1JPtP 3043, 2JPP 21) and 10.5 (d, 1JPtP 3366, 2JPP 21).
1H, δ 7.7–6.2 (m, aromatic), 2.89 (2H, q, CH2), 1.17 (3H, t, CH3).
[Pt{TolSO2NC(S)NCH2CH=CH2}(PPh3)2] 2h. Pale yellow solid. M.p.
226–230 ◦C. ESI MS: m/z [M + H]+ 989.27 (calculated, 989.18), [M +
Na]+ 1010.11 (calculated, 1010.17). FTIR (cmꢀ 1): 1633(w, br), 1500(s),
1436(m), 1141(m), 1091(s), 693(s). NMR: 31P{1H}, δ (ppm) 17.3 (d,
1JPtP 3038, 2JPP 21) and 12.1 (d, 1JPtP 3308, 2JPP 21). 1H, δ 7.8 (Tol, d,
2H), 7.78 (Tol, d, 2H), 7.5–7.0 (PPh3, m, 30H), 5.2 (allyl-CH, m, 1H), 4.5
References
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