2.1. Preparation and Identification of Platinathiiranes 3a–d
Materials and Techniques. The
1H and
13C{
1H} spectra were recorded with a Bruker Avance 200 MHz spectrometer (Terre Haute, IN, USA). Chemical shifts are given in parts per million with reference to internal SiMe
4 or CHCl
3. The mass spectrum was recorded with a Finnigan MAT SSQ 710 instrument (Auburn, CA, USA). The IR spectra were measured with a Perkin–Elmer System 2000 FT-IR spectrometer (Waltham, MA, USA). Elemental analysis was performed with a Leco CHNS-932 apparatus (Madrid, Spain). Silica gel 60 (0.015–0.040 mm) was used for column chromatography, and thin layer chromatography (TLC) was performed by using Merck (Kenilworth, NJ, USA) TLC aluminum sheets (Silica gel 60 F254). Solvents from Fisher Scientific (Ottawa, Ontario, Canada) and other chemicals from Acros were used without further purification. All solvents were dried and distilled prior to the use according to standard methods. The starting materials were prepared according to literature procedures [
9,
18,
20].
General procedure: To a stirred solution of 0.063 mmole (bisphosphane)Pt(nbe) 2a–c [
20] in 15 mL toluene one equivalent of thioketone
1a (or
1b) in toluene (10 mL) was added dropwise, whereupon the color of the solution changed. The mixture was stirred overnight at room temperature. Then, the solvent was removed under reduced pressure at room temperature and the solid residue was washed three to four times with diethylether. Next, the residue was dissolved in a small amount of toluene and subsequent diffusion of
n-pentane into this concentrated solution gave crystals of complexes
3a–
d suitable for SC-X-ray diffraction. Structures of the synthesized complexes
3 are shown in
Figure 2.
(dppbe)Pt(2-diferrocenylthioketone) 3a. Orange colored crystals, yield: 61 mg (91%).1H (CD2Cl2, 400 MHz): 7.75 (m, 1H, dppbe), 7.65 (m, 5H, dppbe), 7.47 (m, 2H, dppbe), 7.39 (m, 6H, dppbe), 7.33 (m, 2H, dppbe), 7.23 (m, 8H, dppbe), 3.92 (m, 12H, 10H C5H5 and 2H C5H4), 3.85 (m, 2H, C5H4), 3.82 (m, 2H, C5H4), 3.75 (m, 2H, C5H4).13C{1H} (101 MHz, CD2Cl2): 134.1 (m) 133.9 (m), 133.6 (m), 133.1 (m), 132.7 (m), 131.8 (m), 131.2 (m), 130.6 (m), 130.2 (m), 128.9 (m), 128.6 (m), 102.9 (m, S=CFc2), 70.3 (m), 69.7 (m), 69.4 (s, C5H5), 69.3 (m), 66.5 (s (C5H4), 66.3 (s, C5H4).31P{1H} NMR (CD2Cl2,162 MHz): 42.79 (d with 195Pt sat., 1JPPt = 2835.0, 2JPP = 28.1 Hz), 36.52 (d with 195Pt sat., 1JPPt = 4167.2, 2JPP = 28.0 Hz).195Pt{1H} (CD2Cl2, 129 MHz): −5059 (dd, 1JPtP = 4168 Hz, 1JPtP = 2835 MHz). ESI-MS(+mode) m/z: 1054.8 [M-2H]+ (including isotope pattern as calculated). EA: C51H42Fe2P2PtS∙0.5 toluene∙0.25 pentane (calc./found): C: 59.80/59.71; H: 4.41/4.40; S: 2.86/2.65.
(dppn)Pt(2-diferrocenylthioketone) 3b. Orange colored crystals, yield: 47 mg (68%).1H (CD2Cl2, 400 MHz): 8.05 (m, 2H, o-H of dppn bridge), 7.42 (m, 2H, CHar), 7.33 (m, 2H, CHar), 7.25 (m, 8H, o-/m-C6H5), 7.14 (m, 8H, o-/m-C6H5), 6.91 (m, 4H, CHar), 6.58 (CHar), 4.20 (m, 10H, Cp C5H5), 4.12 (m, 2H, Cp C5H4) 3.97 (m, 2H, Cp C5H4), 3.90 (m, 2H, Cp C5H4), 3.85 (m, 2H, Cp C5H4). 13C{1H} (CD2Cl2, 101 MHz): 134.0 (m), 133.6 (m), 133.3 (m), 130.0 (m), 129.6 (m), 129.6 (m), 128.3 (m), 127.9 (m), 125.5 (m), 70.3 (m), 69.4 (m), 66.1 (m), 65.8 (m). 31P{1H} (CD2Cl2, 162 MHz): 4.63 (d with 195Pt sat. 1JPPt = 2704 Hz, 2JPP = 22.5 Hz), 4.26 (d with 195Pt sat. 1JPPt = 3970 Hz, 2JPP = 22.5 Hz). ESI-MS(+mode) m/z: 1104.6 [M-H]+ (including isotope pattern as calculated minus H). EA: C55H44Fe2P2PtS∙0.5 toluene∙0.25 pentane (calc./found): C: 59.74/59.15, H: 4.01/3.95, S: 2.90/2.62.
(dppf)Pt(2-diferrocenylthioketone) 3c. Orange colored crystals, yield: 41 mg (56%). 1H (CD2Cl2, 400 MHz): 8.01 (m, 4H, C6H5ar), 7.5 (m, 6H, C6H5), 7.24 (m, 2H, C6H5), 7.03 (m, 8H, C6H5), 4.34 (m, 4H, C5H4), 4.19 (m, 12H, C5H4/C5H5), 4.09 (m, 2H, C5H4), 3.83 (m, 4H, C5H4), 3.74 (m, 2H, C5H4), 3.66 (m, 2H, C5H4). 13C{1H} (CD2Cl2, 101 MHz): 135.7 (s), 134.8–134.4 (m), 130.4 (m), 129.8 (m), 129.3 (m), 128.4 (m), 127.7 (m), 100.3 (m), 76.1 (m), 74.7 (m), 72.9 (m), 71.4 (m), 70.9 (m), 70.3 (m), 69.9 (m), 69.5 (m), 69.3 (m), 65.8 (m). 31P{1H} (CD2Cl2, 162 MHz): 17.66 (s with 195Pt sat. 1JPPt = 4599 Hz), 14.14 (s with 195Pt sat. 1JPPt = 3970 Hz). 195Pt{1H} (CD2Cl2, 129 MHz): −4900 (dd, 1JPtP = 4597 Hz, 1JPtP = 3117 MHz). ESI-MS(+mode) m/z: 1161.6 [M-2H]+ (including isotope pattern as calculated minus 2H). EA: C55H46Fe3P2PtS∙0.25 toluene (calc./found): C: 57.44/57.76; H: 4.08/4.11; S: 2.70/2.76.
(dppf)Pt(2-thiobenzophenone) 3d. Colorless crystals, yield: 51 mg (85%). 1H (600 MHz, CD2Cl2): 7.91–7.83 (m, 4 H, CHar), 7.45 (m, 6 H, CHar), 7.29–7.20 (m, 6 H, CHar), 7.05 (m, 8 H, CHar), 6.92 (m, 4 H, CHar), 6.89–6.85 (m, 2 H, CHar), 4.16 (m, 12 H, C5H4 of cp). 13C{1H} (151 MHz, CD2Cl2): 134.7 (Car), 134.7 (Car), 134.4 (Car), 134.4 (Car), 130.5 (Car), 130.1 (Car), 130.1 (Car), 128.5 (Car), 128.4 (Car), 128.0 (Car), 127.9 (Car), 127.1 (Car), 124.2 (Car), 75.9 (m, CCp), 75.0 (s, CCp), 73.0 (m, CCp), 72.1 (s, CCp). 31P{1H} (243 MHz, CD2Cl2): 18,82 (s with 195Pt-sat 1J(PPt) = 4508 Hz), 17.64 (s with 195Pt-sat 1J(PPt) = 3135 Hz) P–P coupling not resolute. 195Pt{1H} (129 MHz, CD2Cl2): -4988 (dd, 1J(PPt) = 4511, 3132 Hz). MS (DEI): m/z (%) = 947 [M+] (8), 749 [M+-thioketone] (28), 198 [thioketone+] (98), 186 [ferrocene+] (99), 185 [diphenylphosphane+] (99), 165 [thioketone+-S] (100), 121 [thioketone+-phenyl] (100), 108 [phenylphosphane+] (99), 77 [phenyl+] (99). EA: C47H38FeP2PtS∙0,5CD2Cl2 (calc/found): C: 57.56/57.80; H, 4.07/4.30; S, 3.23/3,60.