Proton Lability in Highly Hindered Dinuclear
Palladium(I) μ-Phosphido−Secondary Phosphine
Complexes. Crystal Structures of
[Pd2(μ-PBut2)(PCy2H)3(CO)]BF4 and
[Pd2(μ-PBut2)(PCy2H)2(μ,η2,η2-isoprene)]BF4

Leoni, Piero; Pasquali, Marco; Sommovigo, Milena; Albinati, Alberto; Pregosin, Paul S.; Rüegger, Heinz

doi:10.1021/om9509148.s001

Proton Lability in Highly Hindered Dinuclear Palladium(I) μ-Phosphido−Secondary Phosphine Complexes. Crystal Structures of [Pd₂(μ-PBu^t₂)(PCy₂H)₃(CO)]BF₄ and [Pd₂(μ-PBu^t₂)(PCy₂H)₂(μ,η²,η²-isoprene)]BF₄

journal contribution

posted on 1996-04-16, 00:00 authored by Piero Leoni, Marco Pasquali, Milena Sommovigo, Alberto Albinati, Paul S. Pregosin, Heinz Rüegger

The reactions of the dinuclear cationic complexes [Pd₂(μ-PBu^t₂)(PR₃)₄]⁺ (PR₃ = PCy₂H, PMe₃) with CO or isoprene proceed with substitution of one or two phosphine ligands giving the corresponding [Pd₂(μ-PBu^t₂)(PR₃)₃(CO)]⁺ and [Pd₂(μ-PBu^t₂) (μ,η²,η²-isoprene)(PR₃)₂]⁺ cations. [Pd₂(μ-PBu^t₂)(PCy₂H)₃(CO)]⁺ equilibrates in solution to a mixture of monocarbonyl derivatives arising from bridging phosphido/terminal phosphine interchange. The complexes were characterized by multinuclear 1-D and 2-D NMR spectroscopy. The crystal and molecular structures of [Pd₂(μ-PBu^t₂)(PCy₂H)₃(CO)]BF₄ and [Pd₂(μ-PBu^t₂)(PCy₂H)₂(μ,η²,η²-isoprene)]CF₃SO₃ were solved by single-crystal X-ray diffraction studies.