Novel (R2PC2H4PR2)M0−COT Complexes (M = Pd, Pt) Having Semiaromatic η2-COT or 
Dianionic η2(1,4)-COT Ligands

Schager, Frank; Haack, Karl-Josef; Mynott, Richard; Rufinska, Anna; Pörschke, Klaus-Richard

doi:10.1021/om970762b

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Novel (R₂PC₂H₄PR₂)M⁰−COT Complexes (M = Pd, Pt) Having Semiaromatic η²-COT or Dianionic η²(1,4)-COT Ligands

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Schager, Frank
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

Haack, Karl-Josef
Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Mynott, Richard
Service Department Mynott (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Rufinska, Anna
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Pörschke, Klaus-Richard
Research Group Pörschke, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Schager, F., Haack, K.-J., Mynott, R., Rufinska, A., & Pörschke, K.-R. (1998). Novel (R₂PC₂H₄PR₂)M⁰−COT Complexes (M = Pd, Pt) Having Semiaromatic η²-COT or Dianionic η²(1,4)-COT Ligands. Organometallics, 17(5), 807-814. doi:10.1021/om970762b.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0024-2896-8

Abstract

The complexes (R₂PC₂H₄PR₂)Pd(C₂H₄) (R = ⁱPr, ^tBu) react with COT by displacement of the ethene ligand to afford the novel mononuclear complexes (R₂PC₂H₄PR₂)Pd(η²-C₈H₈) (R = ⁱPr (1a), ^tBu (1b)). The COT ligand of 1a,b is semiaromatic; i.e., it is planar with alternating C-C and C=C bonds as expected for the monoanion [C₈H₈]^-. Treatment of 1a,b with (R₂PC₂H₄PR₂)Pd-alkene complexes generates the dinuclear derivatives {(R₂PC₂H₄PR₂)Pd}₂(μ-η²,η²-C₈H₈) (R = ⁱPr (2a), ^tBu(2b)). The complexes 2a,b are labile; elimination of the COT ligand from 2a gives rise to homoleptic Pd₂(μ-dⁱppe)₂. Reaction of (dⁱppe)PtCl₂ with (tmeda)₂Li₂COT or displacement of the alkene ligands in {(dⁱppe)Pt}₂(µ-η²,η²-C₈H₁₂) (4) or (dⁱppe)Pt(C₂H₄) (5) by COT produces (dⁱppe)Pt(η²-C₈H₈) (6a), which in the solid state also has a semiaromatic COT ligand. In solution, complex 6a is in equilibrium with the novel isomeric form (dⁱppe)Pt^II{η²(1,4)-C₈H₈} (6b). The complexes are characterized by IR, MS, and solution and solid-state NMR.