90065-03-5Relevant academic research and scientific papers
Preparation, spectroscopic properties, and reactivity of trans-hydridoaryl and trans-hydridomethyl complexes of platinum(II)
Arnold, Dennis P.,Bennett, Martin A.
, p. 2110 - 2116 (2008/10/08)
trans-Hydridomethyl and trans-hydridoaryl complexes of platinum(II), trans-PtH(R)L2, have been made by three general methods: (1) reaction of hydroxo complexes trans-Pt(OH)RL2 with methanol (R = C6H5, L = P-t-Bu2Me, P-t-BuMe2, PEt3, PPh3; R = CH3, L = P-i-Pr3); (2) treatment of chloro or N-acetamido complexes trans-PtXRL2 (X = Cl, NHCOCH3) with methanolic sodium methoxide or with methanolic or ethanolic sodium borohydride (R = C6H5, L = P-t-Bu2Me, P-t-BuMe2, PPh3, P-i-Pr3; R = CH3, L = PPh3); (3) treatment of labile solvento salts trans-[PtR(solv)L2] BF4 (solv = methanol or acetone) with sodium methoxide or sodium borohydride (R = C6H5, L = PPh3, PEt3, PMe3; R = CH3, L = PPh3). The use of methanol (method 1) or of sodium methoxide (methods 2 and 3) depends on the formation of thermally unstable methoxo complexes trans-Pt(OCH3)RL2, two of which (R = C6H5, L = PEt3; R = CH3, L = PPh3) have been isolated in an impure state and identified spectroscopically. In two cases, the product from NaBH4 reduction is contaminated with a thermally unstable trihydridoplatinum(IV) complex PtH3(R)L2 (R = C6H5; L = PEt3, PMe3). In contrast with the behavior of the corresponding cis isomers, reductive elimination of RH from trans-PtH(R)L2 occurs only at elevated temperature, stability to heat and air being greater for complexes containing bulky phosphines. Loss of benzene from trans-PtH(C6H5)(PEt3)2 is facilitated by CO and inhibited by triethylphosphine. Dimethyl acetylenedicarboxylate inserts into the Pt-H bond of trans-PtH(C6H4-p-Br)(PEt3)2 to give the σ-vinyl complex trans-Pt[Z-C(CO2Me)=CH(CO2Me)](C6H 4-p-Br)(PEt3)2, but olefins such as ethylene, diethyl maleate, and acrylonitrile do not react. Acetonitrile reacts with trans-PtH(C6H5)(PMe3)2 to give benzene and trans-PtH(CH2CN)(PMe3)2 as the main products, probably via an intermediate platinum(IV) oxidative-addition product, and trimethyltin hydride oxidatively adds to trans-PtH(C6H5)(PEt3)2 at -78°C to give a thermally unstable platinum(IV) complex, PtH2(C6H5)(SnMe3)(PEt 3)2, as a mixture of two isomers, identified by their 1H and 31P NMR spectra.
