13985-90-5Relevant academic research and scientific papers
BOND ENERGIES AND THERMAL DECOMPOSITION OF 2> COMPLEXES
Morvillo, A.,Favero, G.,Turco, A.
, p. 111 - 118 (1983)
The thermal decomposition of the complexes trans- (L = P(C2H5)3; X = Cl, Br, I, CN) in decalin at 170 and 200 deg affords methane, platinum metal and .The kinetics of the decomposition of the complexes were determined by monitoring the appearance of methane by GLC.The observed first-order rate constant was found to be independent on the nature of the ligand X.The thermal decomposition of the trideuteriomethyl complexes (X = I, CN) in decalin-d18 at 170 and 200 deg C was studied by GLC/MS.The thermolysis affords CD3H and CD4 in ratios which are independent of the nature of X and of the temperature used.The mass spectra of the complexes were also examined.A relative scale of platinum-to-methyl bond dissociation energies has been established by measuring the appearance potential of the fragment ion + and the ionization energies in the series .Ionization potentials and Pt-CH3 bond energies show a clear dependence on the nature of X which is not reflected in corresponding changes in the decomposition rates.
High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes
Raphael Karikachery, Alice,Lee, Han Baek,Masjedi, Mehdi,Ross, Andreas,Moody, Morgan A.,Cai, Xiaochen,Chui, Megan,Hoff, Carl D.,Sharp, Paul R.
, p. 4113 - 4119 (2013/05/09)
Pt(IV) complexes trans-Pt(PEt3)2(R)(Br)3 (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.
