709046-45-7Relevant academic research and scientific papers
Regioselective HON-addition of bifunctional hydrazone oximes to Pt(IV)-bound nitriles
Garnovskii, Dmitrii A.,Pombeiro, Armando J.L.,Haukka, Matti,Sobota, Piotr,Kukushkin, Vadim Yu.
, p. 1097 - 1103 (2004)
Treatment of frans-[PtCl4(RCN)2] (R = Me, Et) with the hydrazone oximes MeC(=NOH)C(R′)=NNH2 (R′ = Me, Ph) at 45°C in CH2Cl2 led to the formation of trans-[PtCl4{NH=C(R)ON=C(Me)C(R′)=NNH2} 2] (R/R′ = Me/Ph 1, Et/ Me 2, Et/Ph 3) due to the regioselective OH-addition of the bifunctional MeC(=NOH)C(R′)=NNH 2 to the nitrile group. The reaction of 3 and Ph3P= CHCO2Me allows the formation of the Pt(II) complex trans-[PtCl 2{NH= C(Et)ON=C(Me)C(Ph)=NNH2}2] (4). In 4, the imine ligand was liberated by substitution with 2 equivalents of bis(1,2-diphenylphosphino)ethane (dppe) in CDCl3 to give, along with the free ligand, the solid [Pt(dppe)2]Cl2. The free iminoacyl hydrazone, having a restricted life-time, decomposes at 20-25°C in about 20 h to the parent organonitrile and the hydrazone oxime. The Schiff condensation of the free NH2 groups of 4 with aromatic aldehydes, i.e. 2-OH-5-NO2-benzaldehyde and 4-NO2-benzaldehyde, brings about the formation of the platinum(II) complexes trans-[PtCl 2{NH=C(Et)ON=C(Me)C(Ph)=NN=CH(C6H3-2-OH-5- NO2}2] (5) and trans-[PtCl2{NH= C(Et)ON=C(Me)C(Ph)=NN=CH(C6H4-4-NO2} 2] (6), respectively, containing functionalized remote peripherical groups. Metallization of 5, which can be considered as a novel type of metallaligand, was achieved by its reaction with M(OAc) 2·nH2O (M = Cu, n= 2; M = Co, n = 4) in a 1: 1 molar ratio furnishing solid heteronuclear compounds with composition [Pt]: [M] = 1: 1. The complexes were characterized by C, H, N elemental analyses, FAB - mass-spectrometry, IR, 1H, 13C{1H and 195Pt NMR spectroscopies; X-ray structures were determined for 3, 4 and 5.
