Dalton Transactions
Paper
(2 × 3 mL) to obtain a pale yellow solid (159 mg) in 84% yield. vided by the Integrated Screening Platform of Toulouse (PICT,
Crystallization from THF at 6 °C gave yellow crystals suitable for IBiSA).
the X-ray study. M.p.: 103 °C; 1H NMR (300.18 MHz, C6D6,
25 °C): δ 1.28 (s, 18H, C(CH3)3); 1.46 (d, 3JHH = 6.3 Hz, 12H, CH
3
3
(CH3)2); 1.56 (d, JHH = 6.3 Hz, 6H, CH(CH3)2); 1.58 (d, JHH
=
=
2
6.3 Hz, 6H, CH(CH3)2); 1.99 (s, 6H, p-CH3); 2.90 (d, 2H, JHH
Notes and references
13.8 Hz, GeCH2SO); 3.35 (d, 2H, 2JHH = 13.8 Hz, GeCH2SO); 4.27
3
3
(sept., JHH = 6.3 Hz, 2H, CH(CH3)2); 4.37 (sept., JHH = 6.3 Hz,
2H, CH(CH3)2); 6.88 (d, 4H, JHH = 8.2 Hz, CHAr); 7.53 (d, 4H,
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3
3JHH = 8.2 Hz, CHAr). 13C{1H} NMR (75.48 MHz, C6D6, 25 °C): δ
21.1 (p-CH3); 23.2 (CH(CH3)2); 23.4 (CH(CH3)2); 26.2 (CH
(CH3)2); 26.4 (CH(CH3)2); 29.3 (C(CH3)3); 39.8 (C(CH3)3); 47.9
(CH(CH3)2); 50.0 (CH(CH3)2); 59.8 (GeCH2SO); 123.7 (CAr); 129.9
(CAr); 139.7 (CAr/q); 148.4 (CAr/q); 174.8 (N–C–N); 216.5 (CO). IR
(Nujol, cm−1): 2021 (s) (CO), 1999 (s) (CO), 1905 (s) (CO), 1015
(med) (SO). MS m/z (%): 1026 ([M+).
Synthesis of (3a). Germylene–sulfoxide 1a (151 mg,
0.38 mmol, 1eq.) with tris(triphenylphosphine)ruthenium(II)
dichloride (364 mg, 0.38 mmol, 1eq.) in THF (5 mL) was
stirred for 15 hours at room temperature. Then, the mixture
was filtered and the solvent was removed under reduced
pressure in order to obtain a red solid. Finally, the resulting
solid was washed with diethyl ether (3 × 5 mL) to afford a red
solid (240 mg). M.p.: 145 °C (decomposition); 1H NMR
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(300.18 MHz, C6D6): δ 0.78 (d, JHH = 6.3 Hz, 3H, CH(CH3)2);
3
0.88 (d, JHH = 6.3 Hz, 3H, CH(CH3)2); 0.94 (s, 9H, C(CH3)3);
3
3
1.09 (d, JHH = 6.3 Hz, 3H, CH(CH3)2); 1.35 (d, JHH = 6.3 Hz,
3H, CH(CH3)2); 2.86 (d, 1H, 2JHH = 13.8 Hz, GeCH2SO); 3.61 (d,
2
3
1H, JHH = 13.8 Hz, GeCH2SO); 3.69 (sept., JHH = 6.3 Hz, 2H,
CH(CH3)2); 6.90 (m, 3H, CHAr(sulfoxide)); 7.09 (m, 19H, CHAr
(phosphine)); 7.45 (m, 2H, CHAr(sulfoxide)); 7.93 (m, 11H, CHAr
(phosphine)). 13C{1H} NMR (75.48 MHz, C6D6): δ 24.0 (CH(CH3)2);
24.8 (CH(CH3)2); 25.0 (CH(CH3)2); 25.5 (CH(CH3)2); 29.2
(C(CH3)3); 38.9 (C(CH3)3); 47.5 (CH(CH3)2); 47.9 (CH(CH3)2);
49.2 (GeCH2SO); 125.8 (CAr(sulfoxide)); 127.0 (3JPC = 9.0 Hz,
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Ar(phosphine)); 128.7 (CAr(phosphine)); 128.9 (CAr(sulfoxide)); 125.8
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(CAr(sulfoxide)); 134.2 (2JPC = 19.6 Hz, CAr(phosphine)); 138.0 (1JPC
=
12.2 Hz, CAr/q(phosphine)); 144.2 (CAr/q(sulfoxide)); 175.5 (N–C–N).
31P NMR (121.49 MHz, C6D6): δ 24.5 (br, Ru-PPh3); 55.5 (br,
Ru-PPh3). MS m/z (%): 830 (M − PPh3), 795 (M − (PPh3 + Cl)),
760 (M − (PPh3 + Cl + Cl)). IR (Nujol, cm−1): 934 (med) (SO).
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the Centre National de la 11 (a) M. El Ezzi, R. Lenk, D. Madec, J.-M. Sotiropoulos,
Recherche Scientifique (CNRS), the Université de Toulouse
(UPS). N. L. is grateful to the Ministère de l’Enseignement
Supérieur et de la Recherche for fellowships. We thank
Isabelle Fabing for technical assistance on equipment pro-
S. Mallet-Ladeira and A. Castel, Angew. Chem., Int. Ed.,
2015, 54, 805–808; (b) N. Deak, P. M. Petrar, S. Mallet-
Ladeira, L. Silaghi-Dumitrescu, G. Nemes and D. Madec,
Chem.
–
Eur. J., 2016, 22, 1349–1354; (c) N. Deak,
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Dalton Trans., 2018, 47, 15751–15756 | 15755