17567-35-0Relevant articles and documents
THE SYNTHESIS, CHARACTERIZATION AND REACTIONS OF A BINUCLEAR TETRAMETHYLPLATINUM(IV) COMPLEX
Lashanizadehgan, Marym,Rashidi, Mehdi,Hux, Janet E.,Puddephatt, Richard J.,Ling, Samson S. M.
, p. 317 - 322 (1984)
Reaction of excess MeLi and MeI with gives the first binuclear tetramethylplatinum(IV) complex .The characterization of this complex, and its reactions with donor ligands to give cis- (L2 = Ph2PCH2PPh2, Ph2PCH2CH2PPh2, 2,2'-bipyridyl, 1,10-phenanthroline or L = PMe2Ph, PMePh2) are described.
Synthesis and reactivity of new κ2-[P,N]Pt(II) complexes of diisopropylphosphino-substituted 2-dimethylaminoindene
Wile, Bradley M.,McDonald, Robert,Ferguson, Michael J.,Stradiotto, Mark
, p. 1959 - 1965 (2008/10/09)
Treatment of 1-PiPr2-2-NMe2-indene (la[H]) with either czs/trans-(SMe2)2PtCl2 or PtCl2 provided (κ22-P,N-2-NMe2-3-P iPr2-indene)PtCl2 (2) in 84% and 55% yield, respectively, while the reaction of 1a[H] with (η4-COD)PtClMe afforded (κ2-P,N-2-NMe2-3-PiPr 2-indene)PtClMe (3) in 91% yield. Whereas in the formation of 2 and 3 the ligand precursor 1a[H] undergoes a rearrangement to give a coordinated 2-NMe2-3-PiPr2-indene (1b[H]) ligand, 1a[H] reacted cleanly with 0.5 equiv of [(μ-SMe2)PtMe2] 2 to give (κ2-P,N-1a[H])PtMe2 (4a) in 97% yield. The isomerization of 4a to (κ2-P,N-1b[H])PtMe 2 (4b) in a THF/iPrOH mixture is rapid and allowed for the isolation of 4b in 99% yield. Heating of 4a in CH2Cl2 resulted in the quantitative formation of 3, while the thermolysis of 4a in toluene in the presence of SMe2 afforded 5, the apparent product of intramolecular C-H activation of an NMe group. The reactivity of 4a with a variety of other two-electron donors, as well as E-H-containing substrates (E = main group fragment), is reported. Although NMR spectroscopic evidence indicated the formation of an intermediate of the type (κ2-P,N-1[H]) Pt(SnPh3)(Me), as well as Ph6Sn2, in the reaction of 4a with 10 equiv of Ph3SnH, negligible conversion of Ph3SnH to Ph6Sn2 was obtained when employing 1 mol % 4a as a catalyst. Single-crystal X-ray diffraction data for 2 and 5 are reported.
C-Pt(IV) activation in new trimethylplatinum(IV) complexes: Nucleophilic attack at metal-carbon bond
Romero, Patricio,Valderrama, Mauricio,Contreras, Raúl,Boys, Daphne
, p. 102 - 110 (2007/10/03)
Reaction of the tetranuclear complex [Me3PtI]4 with the ligand o-Ph2P(E)C6H4SMe (E=S, Se) in a 1:4 molar ratio yields the mononuclear neutral complexes [Me3PtI{η2-MeSC6 H4P(E) Ph2-S,S}] (E=S(1), Se(2)). Iodide abstraction from these compounds with AgPF6 in the presence of a ligand L (PPh3, py) leads to cationic complexes of the type [Me3Pt(η2-MeSC6H4P(E) Ph2-E,S)L]PF6 [E=S, L=PPh3 (3), Py (4); E=Se, L=Py (5)]. However, using complex 2 and the ligand PPh3 under identical conditions induces a reductive elimination reaction affording the Pt(II) complex [MePt(η2-MeSC6 H4PPh2- P,S)(PPh3)]PF6 (6). Reactions of complexes 3 and 4 with NaI reveal a nucleophilic attack of the iodide to one of the methyl groups bonded to the platinum center generating a series of subsequent side reactions. Complex [Me3Pt{η2- MeSC6H4P(S) Ph2-S,S}(py)]PF6 ·CH2 Cl2 (4) was additionally characterised by X-ray diffraction. The platinum atom exhibits a distorted octahedral coordination, bonded to three methyl carbon atoms in a facial arrangement; a bidentate chelate S,S′-bonded ligand and a nitrogen atom of the pyridine ligand complete the metal coordination sphere.
