Addition of hydroxide, alkoxide, and carboxylate anions to platinum-bonded ethylene

Abstract

The cation [ Pt(q2-C,H,)CI(tmen)] + (1) (tmen = N,N,N',N'-tetramethylethylenediamine) reacts with water and alcohol under basic conditions t o give nucleophilic addition of hydroxide and alkoxide anions to ethylene and formation of [Pt(CH,CH,OH)CI( tmen)] (4) and [Pt(CH,CH,OR)Cl(tmen)] [R = M e (2) or Et (3)] respectively. Compound (4), either in solution or in the solid, undergoes a condensation reaction with formation of [ (trnen)CIPt(CH,CH,OCH,CH,) PtCl(tmen)] (5). Compound (1 ) reacts also with excess of acetate in water t o give the ester complex [ Pt{CH,-CH,OC(O) Me}CI(tmen)] (6). Compound (6), in the solid state, slowly dissociates to acetate anion and cation ( I ) , redissolution in chloroform restoring the original species. Compounds (3)-(6), dissolved in methanol, are transformed into (2).

New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species

“…Comparing the reactivity of 3b, 3c with that of 3a previously investigated, 6j,l,7m-o, [14][15][16]18,25 it can be concluded that in the former complexes the electrophilicity of the coordinated ethene is fully retained (as confirmed by the ability to add tertiary amines 25 ). The platinum atom, however, competes more efficiently with the olefin for addition of soft nuceophiles (such as carbanions).…”

Nucleophilic Attack of Carbonyl-Stabilized Phosphorus Ylides on 1,5-Cyclooctadiene Complexes of Palladium and Platinum

“…Nucleophilic attack at olefinic bonds coordinated to palladium(II) or platinum(II) has been well studied , and found to be the key step in many catalytic reactions. A wide range of nucleophiles including HO - , , RO - , , RCO 2 - , ,, N 3 - , , H - , Cl - , , NR n H 3 - n , , CN - , NCO - , ,, NO 2 - , ,,, aryl, ,,− acetylacetonate, , diethylmalonate, ethyl acetoacetate, and N , N -dimethylaminonaphthalene (Proton Sponge) have been employed, and enhanced electrophilicity of the olefinic moiety in cationic complexes has been observed . Although phosphorus ylides have never been used in these reactions, a couple of examples were reported in which an (ethylene)iron(II) complex was attacked by an ylide to give a metalated phosphonium complex. , In most cases the attack is produced in an exo fashion to give complexes in which the nucleophile is anti with respect to the metal.…”

Platinum(II) complexes with tris(2-carboxyethyl)phosphine, X-ray structure and reactions with polar solvents and glutathione

“…Complexes cis-[PtCl 2 (CH 3 CN) 2 ] and trans-[PtCl 2 (CH 3 CN) 2 ] were prepared according to the reported method [26]. Infrared spectra (KBr pellets and nujol) were recorded with a Bruker IFS 113v and Bruker 66/s spectrometers, 1 H, 13 C, 31 P and 195 Pt NMR spectra on a Bruker AMX 300 and Bruker Avance 500 spectrometers.…”