62075-38-1Relevant academic research and scientific papers
Bis(carboxylato) complexes of platinum(II). Structural and bonding analysis of [Pt(O2CR)2(L-L)] [L-L = 2PPh3, Ph2PCH2PPh2 or Fe(C5H4PPh2)2; R = Me, CF3, Pri or Ph]
Tan, Agnes L.,Low, Pauline M. N.,Zhou, Zhong-Yuan,Zheng, Weiming,Wu, Bo-Mu,Mak, Thomas C. W.,Hor, T. S. Andy
, p. 2207 - 2214 (2007/10/03)
Treatment of [PtCl2(L-L)] [L-L = 2 PPh3, Ph2PCH2PPh2(dppm) or Fe(C5H4PPh2)2(dppf)] with Ag(O2CR) (R = Me, CF3, Pri or Ph) at room temperature generally gave [Pt(O2CR)2(L-L)] in moderate to good yields. The crystal and molecular structures of [Pt(O2CMe)2(dppf)]·H2O, [Pt(O2CPh)2(dppf)]·CH2Cl2 and [Pt(O2CCF3)2(dppm)] have been determined by single-crystal X-ray diffractometry. All these complexes show a mononuclear square-planar structure with a chelating diphosphine and two neighbouring (cis) carboxylates in a monodentate mode. These structures contrast those of the parent [Pt4(μ-O2CMe)8] and its derivative [Pt4(en)4(μ-O2CMe)4]4+ (en = ethylenediamine) which are tetrameric, based on octahedral PtII, and contain bridging acetates and direct Pt-Pt bonds. Fenske-Hall molecular orbital calculations of these structures confirmed the existence of Pt-Pt bonding interactions. The presence of hard and electronegative ligands like en and acetate incurs a deficiency in σ-electron density, compared to virtually filled non-bonding orbitals; the former is alleviated by Pt-Pt bonding, d8 Complexes with ligands like phosphines possessing both σ-donating and π-accepting qualities appear to favour the usual square-planar geometry.
Insertion of Carbon Dioxide, of CO2-like Molecules, and of Other Unsaturated Compounds into the Platinum-Nitrogen Bond of
Cenini, Sergio,Porta, Francesca,Pizzotti, Maddalena,Crotti, Corrado
, p. 163 - 168 (2007/10/02)
The compound (1) reacts reversibly with carbon dioxide to give (2).Other CO2-like molecules readily and irreversibly insert into the platinum-nitrogen bond of (1); with CS2, PhNCO, and PhNCS the corresponding 1:1 adducts (3), (4), and (5), respectively have been obtained.Compound (2) is an isomer of the insertion product (6), , obtained from the reaction of with PhNCO.A labile insertion product, , (7), was obtained by reaction of (1) with PhCHO, while no reaction was observed between (1) and acetone or diethyl carbonate.However, compound (1) reacts with EtO2C-N=N-CO2Et to give the substitution product (8), .The reactions of compound (2) towards mineral acids, organic acids, benzoyl chloride, and sulphonyl chlorides have been studied.The products are identical to those obtained from the corresponding reactions of (1).I.r., 1H, 31P, and 195Pt n.m.r. spectra of the new compounds are reported and discussed.
