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(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis.
Schmid, Matthias; Oña-Burgos, Pascual; Guillaume, Sophie M; Roesky, Peter W.
Afiliação
  • Schmid M; Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany. roesky@kit.edu.
Dalton Trans ; 44(27): 12338-48, 2015 Jul 21.
Article em En | MEDLINE | ID: mdl-25683468
The (iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh2=NSiMe3)(PPh2=S)}(-) ligand has been used for the synthesis of divalent and trivalent rare-earth borohydride complexes. The salt metathesis of the potassium reagent [K{CH(PPh2=NSiMe3)(PPh2=S)}]2 with [Yb(BH4)2(THF)2] resulted in the divalent monoborohydride ytterbium complex [{CH(PPh2=NSiMe3)(PPh2=S)}Yb(BH4)(THF)2]. The 2D (31)P/(171)Yb HMQC-NMR spectrum clearly showed the coupling between both nuclei. The trivalent bisborohydrides [{CH(PPh2=NSiMe3)(PPh2=S)}Ln(BH4)2(THF)] (Ln = Y, Sm, Tb, Dy, Er, Yb and Lu) were obtained by reaction of [K{CH(PPh2=NSiMe3)(PPh2=S)}]2 with [Ln(BH4)3(THF)3]. All new compounds were characterized by single X-ray diffraction. The divalent and trivalent compounds were next used as initiators in the ring-opening polymerization (ROP) of ε-caprolactone (CL) and trimethylene carbonate (TMC). All complexes afforded a generally well-controlled ROP of both of these cyclic esters. High molar mass poly(ε-caprolactone) diols (Mn,NMR < 101,300 g mol(-1), DM = 1.44), and α,ω-dihydroxy and α-hydroxy,ω-formate telechelic poly(trimethylene carbonate)s (Mn,NMR < 20,000 g mol(-1), DM = 1.61) were thus synthesized under mild operating conditions.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2015 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2015 Tipo de documento: Article