The reactions between allyl compounds CH2 = CHCH(2)Fn bearing electron-withdrawing functional (Fn) groups and cationic {Pt(aryl)(1,10-phenanthroline)}(+) fragments generated in situ are described. The aryl and platinum addition to the terminal and, respectively, internal unsaturated carbon is generally observed. The subsequent H-C-aryl bond activation, followed by HFn elimination affords the ortho organic fragment (Pt)-aryl-CH2CH = CH2 eta(1), eta(2)-chelate to the platinum. This process does not occur when the regiochemistry is of Markownikov type and the Pt-CH2CH(aryl)CH(2)Fn fragment is formed. The described results are compared with those concerning the behaviour of unsubstituted alpha-olefins. The X-ray crystal structure of the title five-coordinate complex shows a distorted tbp arrangement of the ligands with the iodide in the equatorial plane and the unusual axial-equatorial coordination mode of the 1,10-phenanthroline. (c) 2004 Elsevier B.V. All rights reserved.

C-C coupling of aryl groups and allyl derivatives on Pt(Il)-phenanthroline fragments: crystal and molecular structure of the tbp [(eta(1), eta(2)-2-allyl,5-methyl-phenyl)iodo(1,10-phenanthroline) platinum(II)] complex containing the N-N ligand in axial-equatorial coordination mode

ROVIELLO, Giuseppina;
2005-01-01

Abstract

The reactions between allyl compounds CH2 = CHCH(2)Fn bearing electron-withdrawing functional (Fn) groups and cationic {Pt(aryl)(1,10-phenanthroline)}(+) fragments generated in situ are described. The aryl and platinum addition to the terminal and, respectively, internal unsaturated carbon is generally observed. The subsequent H-C-aryl bond activation, followed by HFn elimination affords the ortho organic fragment (Pt)-aryl-CH2CH = CH2 eta(1), eta(2)-chelate to the platinum. This process does not occur when the regiochemistry is of Markownikov type and the Pt-CH2CH(aryl)CH(2)Fn fragment is formed. The described results are compared with those concerning the behaviour of unsubstituted alpha-olefins. The X-ray crystal structure of the title five-coordinate complex shows a distorted tbp arrangement of the ligands with the iodide in the equatorial plane and the unusual axial-equatorial coordination mode of the 1,10-phenanthroline. (c) 2004 Elsevier B.V. All rights reserved.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11367/22493
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