Synthesis of New Ketonyl Palladium(II) and Platinum(II) Complexes with Nitrogen-Donor Ligands. Crystal Structure of [Pt{CH₂C(O)Me}₂(bpy)]

Abstract

Complexes [MCl2L2] (M = Pd, Pt; L2 = 2,2‘-bipyridine (bpy) or Me2N(CH2)2NMe2 (tmeda)) react with ketones MeC(O)R (R = Me, Et) in the presence of bases (Ag2O or M‘OH (M‘ = Na, K)) to give the new types of ketonyl palladium(II) and platinum(II) complexes [M{CH2C(O)R}ClL2] (M = Pd, L2 = N,N,N‘,N‘-tetramethylethylenediamine = tmeda; M = Pt, L2 = 2,2‘-bipyridine = bpy) and [Pt{CH2C(O)R}2L2] (R = Me, Et, L2 = bpy). Oxidative addition of chloroacetone on [Pt(dba)2] in the presence of bpy also yields [Pt{CH2C(O)R}ClL2]. [Pd{CH2C(O)Me}Cl(tmeda)] reacts with PhNHNH2 in the presence of TlOTf (OTf = CF3SO3) to give the cyclometalated complex [Pd{CH2C(Me)NNH(Ph)}(tmeda)]OTf. The crystal structure of [Pt{CH2C(O)Me}2(bpy)] has been determined. The platinum atom is in a distorted square-planar environment. The strong trans influence of the acetonyl ligand promotes the lengthening of both Pt−N bonds (2.082(3) and 2.091(3) Å) with concomitant narrowing of the NPtN bond angle (78.89(13)°).

Role of Dissolved and Molecular Oxygen on Cu and PtCu Alloy Particle Structure during Laser Ablation Synthesis in Liquids

“…This was attributedtoastronger weakening of the particle surface chargei np olar solvents than in less-polar ones. The existence of enolate groups bound on metal oxide surfaces [54,55] or on organometallic complexes [56] of Pt and Pd has been reported in the literature on the basis of IR spectroscopy measurements of acetone. [17] They showed that the presence of chaotropic anions, which have high polarizability, resulted in smaller and more stable particles compared with particless ynthesized in the presence of smalla nions with al ow polarizability (cos- motropes).…”

A Ratiometric Fluorescent Probe for Biological Signaling Molecule H2S: Fast Response and High Selectivity

“…If some condensation is mediated by palladium, we suspect that this occurs as depicted in Scheme (i.e., before the complete transformation of the hydridopalladium enolate into the corresponding aldehyde). Indeed, the formation of palladium enolates from carbonyl compounds requires Pd II complexes 24,25 …”

Gold–Acetonyl Complexes: From Side‐Products to Valuable Synthons

“…A range of synthetic methodologies have been used to form these M–ketonyl derivatives,18, 20 for example, oxidative addition to organometallic compounds of α‐halogen carbonyl compounds21 or epoxides,22 transmetallation reactions promoted by Hg salts18, 23 or reactions of main‐group enolates with electrophilic metal centers 19a. 24 Other methodologies involve reactions of carbonyl compounds with metal‐hydroxide25 or metal‐chloride complexes in the presence of bases, such as Ag 2 O, KOH, and NaOH 20c. 26…”