Technetium diazenido-complexes. Part 2. Substitution chemistry of [TcCl(NNC6H4Cl-4)2(PPh3)2] and the synthesis of technetium diazenido-complexes directly from [NH4][TcO4]
摘要:
The bis(diazenido)technetium(III) complex [TcCl(NNR)2(PPh3)2] (R = C6H4Cl-4) reacted with bidentate ligands L with loss of one diazenide ligand to give [Tc(NNR)L2(PPh3)] (L = S2CNR2) and (TcCl(NNR)L(PPh3)2] (HL = maltol) in high yield. With dianionic tetradentate ligands L' complexes of the type cis-[Tc(NNR)L'(PPh3)] [L' = dianion of N,N'-bis(salicylidene)ethane-1,2-diamine (salen), S(CH2)2NMe(CH2)2NMe(CH2)2S or O2S(CH2)2NMe(CH2)2NMe(CH2)2SO2] were obtained. The crystal structure of the complex with L' = salen has been determined. It shows pseudo-octahedral co-ordination about the Tc with the NNR and PPh3 ligands cis. Direct reaction of [TcO4]- with arylhydrazine hydrochlorides generated a diazenide species in situ which reacts with S2CNR2 to give [TcCl(NNR)2(S2CNR2)2] and 2.2'-bipyridine (bipy) to give [TcCl(NNR)(bipy)2]+ isolated as a BPh4- salt.
Chain transfer agents for RAFT polymerization in aqueous media
申请人:McCormick L. Charles
公开号:US20060111531A1
公开(公告)日:2006-05-25
Polymers and copolymers synthesized by means that yield a narrow range of molecular weights can have different properties than polymers synthesized by conventional means. In order to obtain such polymers, however, polymerization must be controlled. One type of controlled polymerization is the reversible addition-fragmentation chain transfer (RAFT) process, which has characteristics of a living polymerization. The present invention discloses a group of dithioesters and trithioesters suitable as chain transfer agents for RAFT polymerization. The present invention also discloses RAFT polymerizations conducted in aqueous media.