Abstract
The five coordinate organoplatinum complex [Pt(bpy)(cod)(Me)][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine) was obtained reacting [Pt(cod)(Me)Cl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR) and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.
Highlights
From general considerations, five coordinate Pt(II) complexes are a bit unusual
Quite frequently, such pentacoordination is reported for Pt(II) or Pd(II) complexes with olefin ligands, and here, the catalytic relevance is obvious
The title complex [Pt(bpy)(cod)(Me)]+ was studied in detail by multinuclear NMR spectroscopy, as shown in Figures 2–4, allowing the complete assignment of all C and H atoms (Scheme 3)
Summary
Five coordinate Pt(II) complexes are a bit unusual. Due to its d8 configuration and a very strong ligand field (5d element), platinum in the oxidation state +2 has a strong tendency to form square planar coordinated [PtL4]n (n = charge) complexes. Pd(II) analogues comes from their involvement as intermediates in important Pt(II) or Pd(II) catalyzed organometallic transformations [3,21,22,23,24,25,26,27,28] Quite frequently, such pentacoordination is reported for Pt(II) or Pd(II) complexes with olefin ligands, and here, the catalytic relevance is obvious. Reports postulated quite similar species [M(N^N)(cod)Cl]+ (M = Pt or Pd) as intermediates during reactions of [M(diene)Cl2] complexes with N^N ligands in the presence of nucleophiles (Nu), forming complexes [M(en-yl)(N^N)]+ in which a nucleophile has been added to one of the diene double bonds, creating a M–C–Nu sigma bond [74,75,76,77,78,79].
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