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[ N ‐Alkyl‐(2‐pyridyl)methanimine]copper(I) Complexes: Characterisation and Application as Catalysts for Atom‐Transfer Polymerisation
Author(s) -
Haddleton David M.,
Duncalf David J.,
Kukulj Dax,
Crossman Martin C.,
Jackson Stuart G.,
Bon Stefan A. F.,
Clark Andrew J.,
Shooter Andrew J.
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199811)1998:11<1799::aid-ejic1799>3.0.co;2-6
Subject(s) - chemistry , alkyl , substituent , catalysis , copper , polymerization , imine , polymer chemistry , atom transfer radical polymerization , medicinal chemistry , organic chemistry , polymer
The synthesis and characterisation of a series of novel bis(imine)copper(I) complexes and their use in atom‐transfer polymerisation of methyl methacrylate is described. Several N ‐alkyl‐(2‐pyridyl)methanimines (alkyl = n ‐butyl, isobutyl, sec ‐butyl, n ‐propyl) and N ‐( n ‐propyl)‐1‐(2‐pyridyl)ethanimine as ligands have been fully characterised. Three bis[ N ‐alkyl‐(2‐pyridyl)methanimine]copper(I) complexes, [Cu{(C 5 H 4 N)CH=N( i Bu)} 2 ][BF 4 ], [Cu{(C 5 H 4 N)C(CH 3 )=N( n Pr)} 2 ][PF 6 ], and [Cu{(C 5 H 4 N)CH=N( s Bu)} 2 ][BF 4 ] have been structurally characterised; all having a distorted tetrahedral arrangement of co‐ordinating nitrogen atoms surrounding the metal centre. All of the catalysts were found to be effective atom‐transfer polymerisation catalysts for the polymerisation of MMA in hydrocarbon solution. However, it was discovered that the performance of the catalysts containing n ‐alkyl substituents was superior to those containing branched alkyl substituents. The presence of branching in the alkyl substituent results in a reduction of reaction rate and a corresponding broadening of the polydispersity index.