Rollover-Assisted C(sp2)C(sp3) Bond Formation

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 suc...

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Bibliographic Details
Published in:Chemistry : a European journal 2014-04, Vol.20 (18), p.5501-5510
Main Authors: Zucca, Antonio, Maidich, Luca, Canu, Laura, Petretto, Giacomo L., Stoccoro, Sergio, Cinellu, Maria Agostina, Clarkson, Guy J., Rourke, Jonathan P.
Format: Article
Language:English
Subjects:
Activation
bond coupling
Bonding
Chemistry
Heterocyclic compounds
Ligands
NMR spectroscopy
platinum
reductive elimination
Rock
Rollover
rollover cyclometalation
Sequences
Series (mathematics)
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Summary: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)(PR3)] resulted in a rare C(sp2)C(sp3) 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 PR3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of CH bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize. Rock and rollover! Rare cases of C(sp2)C(sp3) bond formation from PtIV cyclometalated complexes are described, through a succession of oxidative addition and reductive elimination reactions, taking advantage of a “rollover”/“retro‐rollover” sequence (see scheme).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201304257