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Group 10 and 11 Metal Boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au⁺) Derived from a Triphosphine−Borane

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Marie Sircoglou^†, Sébastien Bontemps^†, Ghenwa Bouhadir^†, Nathalie Saffon^‡, Karinne Miqueu^§, Weixing Gu, Maxime Mercy, Chun-Hsing Chen, Bruce M. Foxman, Laurent Maron*, Oleg V. Ozerov* and Didier Bourissou*^†

Laboratoire Hétérochimie Fondamentale et Appliquée (UMR−CNRS 5069) and Structure Fédérative Toulousaine en Chimie Moléculaire (FR 2599), Université Paul Sabatier, 118, route de Narbonne, F-31062 Toulouse Cedex 09, France, Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux UMR−CNRS 5254, Equipe “Chimie−Physique”, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 09, France, Department of Chemistry, Brandeis University, MS015, 415 South Street, Waltham, Massachusetts 02454, and the Laboratoire de Physique et Chimie des Nanoobjets (UMR−CNRS 5215), INSA, Université Paul Sabatier, 135, avenue de Rangueil, F-31077 Toulouse Cedex, France

J. Am. Chem. Soc., 2008, 130 (49), pp 16729–16738

DOI: 10.1021/ja8070072

Publication Date (Web): November 13, 2008

, †

Laboratoire Hétérochimie Fondamentale et Appliquée.

, ‡

Structure Fédérative Toulousaine en Chimie Moléculaire.

, §

Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux.

Laboratoire de Physique et Chimie des Nanoobjets.

Brandeis University.

Section:

Inorganic Chemicals and Reactions

Abstract

The ambiphilic triphosphine−borane ligand 1 {TPB = [o-iPr₂P-(C₆H₄)]₃B} readily coordinates to all group 10 and 11 metals to afford a complete series of metal boratranes (TPB)[M] 2−8 (2: M = Ni, 3: M = Pd, 4: M = Pt, 5: M = CuCl, 6: M = AgCl, 7: M = AuCl, 8: M = Au⁺). Spectroscopic and structural characterization unambiguously establishes the presence of M→B interactions in all of these complexes. The first evidence for borane coordination to copper and silver is provided, and the Au→B interaction is shown to persist upon chloride abstraction. Experimental and theoretical considerations indicate that the M→B interaction is strongest in the Pt and Au complexes. The influence of the oxidation state and charge of the metal is substantiated, and the consequences of relativistic effects are discussed. The coordination of the σ-acceptor borane ligand is found to induce a significant bathochromic shift of the UV−vis spectra, the Ni, Pd, and Pt complex presenting strong absorptions in the visible range. In addition, all of the group 10 and 11 metal boratranes adopt C₃ symmetry both in the solid state and in solution. The central M→B interaction is found to moderately influence the degree of helicity and configurational stability of these three-bladed propellers, and DFT calculations support a dissociative pathway for the inversion process.

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