83571-74-8Relevant articles and documents
Metal Complexes of Functionalized Sulfur Containing Ligands, VIII 4-Phenyl-1,2-dithiolane-1-oxide, a Stable, Five-Membered Cyclic Thiosulfinate
Weigand, Wolfgang,Bosl, Gabriele,Dielingen, Bernd von,Gollnick, Klaus
, p. 513 - 518 (2007/10/02)
Sensitized photooxidation of 4-phenyl-1,2-dithiolane 1 has been studied.Reacting it with 0.5 mole equivalents of singlet oxygen, a mixture of 1, 4-phenyl-1,2-dithiolane-1-oxide 2, and 4-phenyl-1,2-dithiolane-2-dioxide 3 is produced.Using one mole equivale
Mechanistic studies of the thermolytic and photolytic rearrangement of [bis(diphenylphosphino)ethane]bis(neophyl)platinum(II)
Ankianiec, Bernardeta C.,Hardy, David T.,Thomson, S. Katherine,Watkins, W. Niall,Young, G. Brent
, p. 2591 - 2598 (2008/10/08)
Comparative mechanistic studies are presented of the thermolytic and photolytic behavior of the bis-(neophyl)platinum(II) derivative Pt(CH2CMe2Ph)2(dppe) (neophyl = 2-methyl-2-phenylpropyl; dppe = 1,2-bis(diphenylphoephino)ethane). Thermolytic rearrangement is less facile than for monodentate P-donor analogues and affords the platinaindan Pt(2-C6H4CMe2CH2)(dppe) by intramolecular aromatic C-H activation and H-transfer to eliminated tert-butylbenzene. The kinetic isotope effect on metallacyclization (kobsH/kobsD = 2.40) and the negative activation entropy (ΔS≠obs = -13 (±4) J·K-1·mol-1) suggest a pathway in which scission of one Pt-P is mechanistically significant but C-H addition to Pt has the most energetic transition state. Photolytic rearrangement in toluene-d0 proceeds by two major paths, both of which involve primary Pt-C homolysis. The resultant neophyl radical may then provide a destination for migrating hydrogen in a cyclometalation of the residual 17-electron organoplatinum species, leading to Pt(2-C6H4CMe2CH2)(dppe). Alternatively, H-abstraction by the neophyl fragment within the solvent cage produces a benzyl radical which recombines with the metal moiety to give Pt(CH2Ph)(CH2Me2Ph)(dppe). This benzylplatinum complex is also photolabile, giving ultimately platinaindan via benzyl radical expulsion. This indirect solvent metalation is not evident during photolysis in toluene-d8 and in benzene.
Photoinduced net [2 + 2 + 2] cycloreversion of platinum(II) glycolate complexes: A new approach to the generation of reduced, coordinatively unsaturated metal species and the activation of carbohydrate carbon-carbon single bonds
Andrews, Mark A.,Gould, George L.
, p. 387 - 389 (2008/10/08)
Photolysis of thermally stable (1,2-bis(diphenylphosphino)ethane)platinum(II) glycolate complexes causes a facile net [2 + 2 + 2] cycloreversion of the 2,5-dioxaplatinacyclopentane moiety to give two organic carbonyl compounds and a reactive (dppe)Pt0 intermediate, as shown by trapping with dppe, ethylene, or hydrogen. Photolysis under hydrogen in the presence of (PPh3)4RuH2 leads to hydrocracking of the glycol carbon-carbon single bond.
Synthesis and Reactivity of Platinum-Formaldehyde Complexes
Head, Robert A.
, p. 1637 - 1640 (2007/10/02)
Sodium dihydronaphthylide reduction of (R3=Et3, Pri3, Ph3, Et2Ph, or 1/2Ph2PCH2CH2PPh2) under an ethylene atmosphere gives in quantitative yield as shown by (31)P n.m.r. spectroscopy.Reactions of the ethylene complexes with CO, CH2I2, (CF3)2CO, (CO2Et)2CO, and CH2O are described.Monomeric formaldehyde reacts to give the first platinum-formaldehyde complexes, , decomposition of which produces (n=3 or 4) and a complex tentatively assigned as .
