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Cabon, Yves; Ricard, Louis; Frison, Gilles; Carmichael, Duncan

A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp2 Hybridised Phosphorus Atom – A System Allowing OH– Mediated Uptake of [MCl2] (M = Pd, Pt) Centres

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  • Medientyp: E-Artikel
  • Titel: A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp2 Hybridised Phosphorus Atom – A System Allowing OH– Mediated Uptake of [MCl2] (M = Pd, Pt) Centres
  • Beteiligte: Cabon, Yves; Ricard, Louis; Frison, Gilles; Carmichael, Duncan
  • Erschienen: Wiley, 2019
  • Erschienen in: European Journal of Inorganic Chemistry, 2019 (2019) 11-12, Seite 1544-1551
  • Sprache: Englisch
  • DOI: 10.1002/ejic.201801181
  • ISSN: 1434-1948; 1099-0682
  • Schlagwörter: Inorganic Chemistry
  • Entstehung:
  • Anmerkungen:
  • Beschreibung: <jats:p>The coordination chemistry of the 1,1′‐diphosphacobaltocenium salt [Co(η<jats:sup>5</jats:sup>‐2‐TBS‐3,4‐Me<jats:sub>2</jats:sub>‐PC<jats:sub>4</jats:sub>H)<jats:sub>2</jats:sub>]<jats:sup>+</jats:sup> BF<jats:sub>4</jats:sub><jats:sup>–</jats:sup> (<jats:italic>rac</jats:italic>‐<jats:bold>1</jats:bold>) and its derivatives with respect to [MCl<jats:sub>2</jats:sub>] (M = Pd, Pt) centres is presented. <jats:italic>Rac</jats:italic>‐<jats:bold>1</jats:bold>, showing two sp<jats:sup>2</jats:sup> hybridised phosphorus atoms and a positive charge, is stable towards strong electrophiles (PhCH<jats:sub>2</jats:sub>Br, MeI), but undergoes attack by hydroxide at phosphorus with subsequent rearrangement to form the neutral conjugate base [Co{η<jats:sup>5</jats:sup>‐(2‐TBS‐3,4‐Me<jats:sub>2</jats:sub>‐PC<jats:sub>4</jats:sub>H)}{η<jats:sup>4</jats:sup>‐(1‐O,1‐H‐2‐TBS‐3,4‐Me<jats:sub>2</jats:sub>‐PC<jats:sub>4</jats:sub>H)}] (<jats:italic>rac</jats:italic>‐<jats:bold>2</jats:bold>). <jats:italic>Rac</jats:italic>‐<jats:bold>1</jats:bold> undergoes reaction with [MCl<jats:sub>2</jats:sub>(PhCN)<jats:sub>2</jats:sub>] (M=Pd, Pt) in damp chloroform to form the P<jats:italic><jats:sub>sp2</jats:sub></jats:italic>–P<jats:italic><jats:sub>sp3</jats:sub></jats:italic> chelating <jats:italic>sec</jats:italic>‐phosphinite complexes [MCl<jats:sub>2</jats:sub>{Co{η<jats:sup>5</jats:sup>‐(2‐TBS‐3,4‐Me<jats:sub>2</jats:sub>‐PC<jats:sub>4</jats:sub>H)}{η<jats:sup>4</jats:sup>‐(1‐OH‐2‐TBS‐3,4‐Me<jats:sub>2</jats:sub>‐PC<jats:sub>4</jats:sub>H)}}] <jats:bold>4</jats:bold> (M = Pd, Pt), which are also accessible directly, but under more forcing conditions, from <jats:italic>rac</jats:italic>‐<jats:bold>2</jats:bold>. Computational analysis (M06/def2‐TZVP) indicates that the conjugate base, in the form of its <jats:italic>sec</jats:italic>‐phosphinite tautomer <jats:italic>rac</jats:italic>‐<jats:bold>3</jats:bold>, shows significantly stronger bonding to the metal centre than does the parent 1,1′‐diphosphacobaltocenium salt <jats:italic>rac</jats:italic>‐<jats:bold>1</jats:bold>. The uptake and subsequent release of a [PtCl<jats:sub>2</jats:sub>] centre as a function of the <jats:italic>p</jats:italic>H of the reaction medium hints at the potential for employing the <jats:italic>rac</jats:italic>‐<jats:bold>1</jats:bold>/<jats:italic>rac</jats:italic>‐<jats:bold>2</jats:bold> ligand acid‐base couple as a <jats:italic>p</jats:italic>H‐driven coordination switch.</jats:p>