Dalton Transactions
Page 18 of 23
DOI: 10.1039/C7DT03599C
PPh3), 7.39ꢀ7.31 (m, 6H, Hm of PPh3), 7.01ꢀ7.95 (m, 2H, H10 and H3′), 6.92 (td, 3JHH = 7.6, 4JHH
= 1.9, 1H, H4′), 6.81 (dd, 3JHH = 7.6, 4JPH = 2.4, 3JPtH = 38.1, 1H, H11), 6.58 (ddd, 3JHH = 4.9, 4JHH
= 1.1, 1H, H5′); 31P{1H} NMR (162 MHz, dmsoꢀd6, 20 °C) δ: 22.10 (s, 1JPtP = 4342, 1P).
[Pt(bzq)(PPh3)(к1-S-SpyN)], 3a.
Yield: 64 mg, 58%; m.p = 281 ◦C. Anal. Calcd for C35H26N3PPtS (746.72): C, 56.30; H, 3.51; N,
1
5.63; Found: C, 56.24; H, 3.58; N, 5.56. H NMR (400 MHz, dmsoꢀd6, 20 °C) δ: 10.10 (m, 3JPtH
= not resolved, 1H, H2), 8.72 (d, 3JHH = 7.8, 1H, H4), 7.97 (d, 3JHH = 4.7, 2H, H4′), 7.92ꢀ7.82 (m,
3H, H6, H7, H3), 7.77ꢀ7.68 (m, 6H, Ho of PPh3), 7.56 (d, 3JHH = 8.0, 1H, H9), 7.45ꢀ7.384 (m, 3H,
Hp of PPh3), 7.378ꢀ7.30 (m, 6H, Hm of PPh3), 6.96 (t, 3JHH = 7.5, 1H, H10), 6.81 (ddd, 3JHH = 7.3,
4JPH = 2.8, 4JHH = 0.7, 3JPtH = not resolved, 1H, H11), 6.66 (t, 3JHH = 4.8, 1H, H5′); 31P{1H} NMR
(162 MHz, dmsoꢀd6, 20 °C) δ: 21.48 (s, 1JPtP = 4376, 1P).
[Pt(ppy)(PPh3)(к1-S-SpyN)], 3b.
Yield: 60 mg, 54%; m.p = 263 ◦C. Anal. Calcd for C33H26N3PPtS (722.70): C, 54.84; H, 3.63; N,
5.81; Found: C, 54.91; H, 3.56; N, 5.76. 1H NMR (400 MHz, dmsoꢀd6, 20 °C) δ: 9.83 (m, 3JPtH
=
3
3
3
not resolved, 1H, H2), 8.18 (d, JHH = 7.8, 1H, H5), 8.10 (t, JHH = 7.8, 1H, H4), 7.98 (d, JHH
=
4.7, 2H, H4'), 7.80 (d, 3JHH = 7.8, 1H, H6), 7.73ꢀ7.64 (m, 6H, Ho of PPh3), 7.50ꢀ7.29 (m, 10H, H3,
Hp and Hm of PPh3), 6.96 (t, 3JHH = 7.5, 1H, H7), 6.66 (t, 3JHH = 4.8, 1H, H8), 6.63 (m, 3JPtH = not
3
resolved, 1H, H9), 6.52 (t, JHH = 7.2,1H, H5'); 31P{1H} NMR (162 MHz, dmsoꢀd6, 20 °C) δ:
22.27 (s, 1JPtP = 4364, 1P).
Crystal Structure Determination and Refinement
Diffraction data were collected on a SuperNova Xꢀray diffraction system equipped with a
CuKα radiation source (λ = 1.54184 Å). The data were collected at 123 K using an Oxford
Instruments Cryojet Cooler for 2a or at 294 K for 1a. The structures were solved by Intrinsic
Phasing using the ShelXT (Sheldrick, 2015) structure solution program43 and refined by Least
Squares using version 2014/7 of ShelXL (Sheldrick, 2015).44 All nonꢀhydrogen atoms were
refined anisotropically. Hydrogen atom positions were calculated geometrically and refined
using the riding model. Details of crystal and structure refinement are listed in Table S1.
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