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Rollover‐Assisted C(sp 2 )C(sp 3 ) Bond Formation
Author(s) -
Zucca Antonio,
Maidich Luca,
Canu Laura,
Petretto Giacomo L.,
Stoccoro Sergio,
Cinellu Maria Agostina,
Clarkson Guy J.,
Rourke Jonathan P.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304257
Subject(s) - denticity , chemistry , quinoline , medicinal chemistry , stereochemistry , platinum , rollover (web design) , catalysis , crystal structure , crystallography , organic chemistry , world wide web , computer science
Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a “rollover”/“retro‐rollover” reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR 3 )] resulted in a rare C(sp 2 )C(sp 3 ) bond formation to give the bidentate nitrogen ligands 3‐methyl‐2,2′‐bipyridine, 3,6‐dimethyl‐2,2′‐bipyridine, and 3‐methyl‐2‐(2′‐pyridyl)‐quinoline, which were isolated and characterized. The nature of the phosphane PR 3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of CH bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize.