Novel W(II) complexes for reversible addition-fragmentation chain transfer (RAFT) polymerizations

Phosphinoyl and Thiophosphinoylcarbodithioates: Synthesis, Molecular Structure, and Application as New Efficient Mediators for RAFT Polymerization

“…[27] In parallel, Chen et al polymerized St and tert-butyl acrylate by using tungstenpentacarbonyl derivatives with benzyl and allyl as leaving R groups. [28] Our first results confirmed that these metallophosphorus-based compounds behave as efficient RAFT agents. It appeared that their efficiency was not altered by varying the nature of the metal center.…”

Synthesis of S-Alkyl Phosphinocarbodithioates with Switch between P(III) and P(V) Derivatives

“…The resonances were calibrated relative to the residual solvent resonances and were reported with positive values downfield from TMS. For all characterized compounds, the peak assignments in the 1 H and 13 C NMR spectra were based on COSY, HSQC, and HMBC 2D experiments. HRMS were obtained from dichloromethane solutions with a Xevo G2 Q TOF spectrometer by the electrospray or chemical ionization method.…”

“…1 H (400 MHz, CDCl 3 ) δ: 7.36−7.18 (5H, m, Ph), 5.17 (1H, qd, 3 J HH = 7.1 Hz, 4 J HP = 1.8 Hz, CHCH 3 ), 1.65 (3H, dd, 3 J HH = 7.1 Hz, 5 J HP = 0.6 Hz, CHCH 3 ), 1.35 (9H, d, 3 J HP = 14.3 Hz, C(CH 3 ) 3 ), 1.27 (9H, d, 3 J HP = 14.3 Hz, C(CH 3 ) 3 ). 13 C{ 1 H} (125 MHz, CDCl 3 ) δ: 239.0 (d, 1 J CP = 45.2 Hz, C(S)S), 140.6 ( Ph C-CHCH 3 ), 128.5 ( Ph CH), 127.8 ( Ph CH), 127.7 ( Ph CH), 47.3 (d, 3 J CP = 1.6 Hz, CHCH 3 ), 37.17 (d, 1 J CP = 55.6 Hz, C(CH 3 ) 3 ), 37.15 (d, 1 J CP = 55.8 Hz, C(CH 3 ) 3 ), 27.17 (C(CH 3 ) 3 ), 27.09 (C(CH 3 ) 3 ), 20.2 (CHCH 3 ). 31 Alternative Synthetic Procedure for 6.…”

“…The phosphacarbodithioate structural motif often acts as bidentate ligand in complexes with ruthenium 7 and iron 8 that mimic certain biological systems. Ru, Fe, Cr, Mo, Mn) [6][7][8]11,12,13,14,15 but, to the best of our knowledge, no carbodithioate ester with an unprotected phosphino group has so far been described. The present contribution addresses the convenient preparation of the first example of a stable compound of general formula t-Bu2PC(S)SR which involves a phosphorus atom with a free lone pair, as well as several t-Bu2P(X)C(S)SR derivatives (X = BH3, O, S, Se) and describes simple protocols for the addition/removal/exchange of the X group.…”

“…The 13 C NMR spectra also give interesting information, particularly in terms of the C(S)S− group resonance (Table 1). Replacing Ph with t-Bu groups on the phosphorus atom from 4 to 5 shows that the carbon chemical shift of the −C(S)S− group remains essentially unchanged (from 230.6 for 4 to 231.1 ppm for 5), while 1 J CP decreases dramatically from 25.9 to 11.8 Hz.…”