ACCEPTED MANUSCRIPT
[dd, 1H, 3J(H4H3) = 8 Hz, 3J(H5H4) = 6 Hz, H4); 8.26 [d, 1H, 3J(H4H3) = 8 Hz, H3); 7.91
[dd, 1H, 3J(H5H6) = 5 Hz, 3J(H5H4) = 6 Hz, H5]; 4.11-4.18 [m, 2H, CH2N]; 3.75-3.81 [m,
2H, CH2O]; 2.76 [s, 3J(PtH) = 40 Hz, PtOMe]; 1.59 [s, 3H, 2J(PtH) = 73 Hz, PtMe trans
N]; 1.50 [s, 3H, 2J(PtH) = 73 Hz, PtMe trans N]. In a separate reaction, a solution of
[PtMe
(L1)] (0.05 g) in CD3OD (1 mL) was allowed to react with air for 2 h. The 1H
2
NMR spectrum was as above except that the PtOMe resonance was absent. EI-MS: m/z
= 428.2. Calc. for C11H15D5N2O3Pt: m/z = 428.1.
[Pt(OH)(OMe)Me
2
(L2a)], 12a, and [Pt(OH)(OMe)Me (L2b)], 12b and 12c
2
This was prepared in a similar way from [PtMe
12c. Anal. Calc. for C12H22N2O3Pt.H2O: C, 31.65; H, 5.31; N, 6.15. Found: C, 31.66; H,
2
(L2a)], as a mixture of isomers 12a –
(L2a)], 12a, δ(1H) = 9.23 [s, 1H,
4.93; N, 5.90%. NMR in CD3OD: [Pt(OH)(OMe)Me
2
3J(PtH) = 30 Hz, Hi]; 8.95 [d, 1H, 3J(PtH6) = 12 Hz, 3J(H6H5) = 5 Hz, H6]; 8.27 [t, 1H,
3J(H4H3) = 3J(H5H4) = 8 Hz, H4); 8.17 [d, 1H, 3J(H4H3) = 8 Hz, H3); 7.86 [dd, 1H,
3J(H5H6) = 5 Hz, 3J(H5H4) = 8 Hz, H5]; 4.21-4.22 [m, 2H, CH2N]; 3.69-3.71 [m, 2H,
CH2O]; 2.73 [s, 3J(PtH) = 36 Hz, PtOMe]; 2.10-2.11 [m, 2H, CH2]; 1.66 [s, 3H, 2J(PtH) =
72 Hz, PtMe trans N]; 1.65 [s, 3H, 2J(PtH) = 73 Hz, PtMe trans N].
[Pt(OH)(OMe)Me
(L2b)], 12b: δ(1H) = 8.76 [d, 1H, 3J(H6H5) = 5 Hz, H6]; 8.10-8.15 [m,
2
2H, H3, H4); 7.77 [dd, 1H, 3J(H5H6) = 5 Hz, 3J(H5H4) = 8 Hz, H5]; 5.59 [s, 1H, Hi]; 4.08,
4.38 [m, 2H, CH2N]; 3.55-3.61 [m, 2H, CH2O]; 2.77 [s, 3J(PtH) = 38 Hz, PtOMe]; 2.10-
2.11 [m, 2H, CH2]; 1.57 [s, 3H, 2J(PtH) = 72 Hz, PtMe trans N]; 1.56 [s, 3H, 2J(PtH) = 73
Hz, PtMe trans N]. [Pt(OH)(OMe)Me
(L2b)], 12c: δ(1H) = 8.78 [d, 1H, 3J(H6H5) = 5
2
Hz, H6]; 8.05-8.15 [m, 2H, H3, H4); 7.68 [dd, 1H, 3J(H5H6) = 5 Hz, 3J(H5H4) = 8 Hz, H5];
5.56 [s, 1H, Hi]; 4.08, 4.38 [m, 2H, CH2N]; 3.55-3.61 [m, 2H, CH2O]; 2.86 [s, 3J(PtH) =
38 Hz, PtOMe]; 2.10-2.11 [m, 2H, CH2]; 1.45 [s, 3H, 2J(PtH) = 72 Hz, PtMe trans N];
1.44 [s, 3H, 2J(PtH) = 73 Hz, PtMe trans N]. The ratio of isomers was approximately
12a:12b:12c = 8:3:2.
[Pt(OH)Me2{OC(Me)=CHCH(2-C5H4N)NHCH2CH2OH}], 13
A solution of [PtMe (L1)] (0.10 g, 0.26 mmol) in acetone (10 mL) was stirred under an
2
atmosphere of O2 for 1 day. The solvent was evaporated and the orange product was
washed with ether and pentane and dried under vacuum. Anal. Calc. for C13H22N2O3Pt:
C, 34.74; H, 4.93; N, 6.23. Found: C, 34.28; H, 4.98; N, 5.79%. NMR in acetone-d6:
δ(1H) = 8.55 [d, 1H, 3J(PtH6) = 24 Hz, 3J(H6H5) = 5 Hz, H6]; 8.03 [dd, 1H, 3J(H4H3) = 8
Hz, 3J(H4H5) = 6 Hz, H4]; 7.52-7.60 [m, 2H, H3,H5]; 4.43 [d, 1H, 3J(HH) = 8 Hz, CHN];
4.18 [d, 1H, 3J(HH) = 8 Hz, CH=CMe]; 3.80-3.87 [m, 2H, CH2N]; 3.62-3.66 [m, 2H,
CH2O]; 2.11 [s, 3H, CMe]; 1.46 [s, 3H, 2J(PtH) = 71 Hz, PtMe]; 1.41 [s, 3H, 2J(PtH) = 74
Hz, PtMe]. In a similar reaction carried out in acetone-d6, the resonance at δ(1H) = 4.43
appeared as a singlet and the CH=CMe and CMe resonances were absent.
4.
Supplementary material
Figure S1. The longer range hydrogen bonding that connects individual chains of
molecules of 9. CCDC 1487251-1487252 contain the supplementary crystallographic
21