Formation of PPh2C6F5 through Phosphido Platinum and/or Palladium(III) Intermediates,

descriptionPublicationkeyboard_double_arrow_right Article 01 Feb 2006 Greece English Publisher:American Chemical Society (ACS)Journal:Organometallics, volume 25, pages 1,084-1,091 (issn: 0276-7333, eissn: 1520-6041,

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Authors: Ara, I.; Chaouche, N.; Fornies, J.; Fortuno, C.; Kribii, A.; Tsipis, A. C.;

doi: 10.1021/om0508029

handle: 10261/19100

Formation of PPh2C6F5 through Phosphido Platinum and/or Palladium(III) Intermediates,

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Abstract

The two-electron oxidation reactions of the neutral [(C6F5)2M(μ-PR2)2M‘(NCCH3)2] (M = M‘ = Pt or Pd, M = Pt, M‘ = Pd) complexes using I2 as oxidant have been investigated by experimental (R = Ph) and electronic structure calculation methods (R = H). It was found that a reductive coupling of PR2 and C6F5 takes place along the reaction pathway for all oxidized complexes. The most salient structural features of the [(C6F5)2Pt(μ-PR2)2Pd(C6F5)2]2-, [(C6F5)2Pd(μ-PR2)2Pd(acac)]-, and [(C6F5)2Pt(μ-PR2)2PtI2] complexes (experimental R = Ph) are reproduced very well by the B3LYP/lanl2dz calculations (R = H).

We thank the Ministerio de Ciencia y Tecnología and Fondos FEDER (Project BQU2002-03997-CO2- 02), the Diputación General de Aragón for its financial support, and the Agencia Española de Cooperación Internacional (Ministerio de Asuntos Exteriores) for a grant to N.Ch.

8 pages, 5 figures, 3 tables.

Peer reviewed

Country

Greece

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Keywords

palladium(ii)-platinum(ii) pentafluorophenyl complexes, ray crystal-structures, c bond, molecular-structure, bu-t, bridging diphenylphosphido ligands, pd-c6f5 bonds, stereoselective oxidative addition, electronic-structures, density-functional theory

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