Journal of the Chemical Society, Dalton Transactions p. 1021 - 1029 (1996)
Update date:2022-08-11
Topics:
Milani, Barbara
Alessio, Enzo
Mestroni, Giovanni
Zangrando, Ennio
Randaccio, Lucio
Consiglio, Giambattista
Two new atropisomeric bidentate nitrogen-donor chelating ligands, namely (-)-(S,S)-3,3′-(1,2-dimethylcthylenedioxy)-2,2′-bipyridine L1 and (+)-(R)-3,3′-(1-methylethylenedioxy)-2,2′-bipyridine L2, have been synthesised and characterised. The crystal structure of L2 confirmed its atropisomeric nature, the dihedral angle between the planes containing the pyridine rings being 50.1(1)°. The interaction of the new compounds, with palladium(II) salts led to the correspbnding:monochelated palladium complexes, [PdL1(O2CCF3)2] 1 and [PdL2(O2CCF3)2] 2, the crystal structures of which have been determined. Both complexes crystallised with two independent molecules in the unit cell. In the two molecules of 1 the ligand L1 is in the same conformation; while for 2 the two independent molecules correspond to two different atropisomers. The co-ordination geometry around palladium is square planar in all the molecules. In the two independent molecules of 1 and 2 the dihedral angle between the pyridine rings is considerably smaller than that observed in free L2. The complexes are very active catalyst precursors in CO-styrene copolymerisation under mild reaction conditions (PCO = 1 atm, 30°C). The inhibiting role of carbon monoxide is evidenced. A low asymmetric induction was observed together with short isotactic sequences in the copolymer chain.
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