Initiating abilities of diphosphine- and diamine-ligated Pd complexes/NaBPh4 systems for C1 polymerization of diazoacetates. Issue 9 (8th February 2023)

• Record Type: Journal Article
• Authors: Shimomoto, Hiroaki; Miyano, Yuto; Kinoshita, Kaito; Itoh, Tomomichi; Ihara, Eiji
• Is Part Of: Polymer chemistry. Volume 14:Issue 9(2023)
• Page Start: 1007
• Page End: 1018
• Publication Date: 2023-02-08
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/d2py01548j
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : (Diamine)Pd(0)(dichlone)/NaBPh4 systems have been revealed to be effective initiators for diazoacetate polymerization, yielding moderately syndiotactic polymers in moderate yields. Abstract : A series of well-defined Pd complexes bearing diphosphines or diamines and a dichloroquinone-derived unit as ligands were newly prepared and their initiating abilities in conjunction with NaBPh4 for the C1 polymerization of diazoacetates were investigated. Among the (diphosphine)Pd(ii )Cl(Cl-quinonyl) complexes examined here, square planar cis (diphosphine: diphenylphosphinoferrocene) and distorted square planar trans (diphosphine: xantphos) complexes with NaBPh4 yielded highly syndiotactic polymers from ethyl diazoacetate despite low polymer yields. A series of Pd(0) complexes bearing a bidentate diamine such as N, N, N ′, N ′-tetramethyl-1, 3-propanediamine and 2, 3-dichloronaphthoquinone in conjunction with NaBPh4 polymerized diazoacetates to afford moderately syndiotactic polymers in moderate yields, indicating that the (diamine)Pd(0)(dichloroquinone) framework could be a promising general platform for an initiating system with high activity and stereoselectivity for the C1 polymerization of diazoacetates.