83719-70-4Relevant academic research and scientific papers
Role of the trichlorostannyl ligand in homogeneous catalysis. 3. Solvent effects on the reactions of cis-[PtCl2(L)(PR3)] and [Pt2(μ-Cl)2Cl2(PR3)2] (L = CO, SMe2; R = Ph, Et) with SnCl2·2H2O
Anderson, Gordon K.,Clark, Howard C.,Davies, Julian A.
, p. 434 - 438 (2008/10/08)
The reactivity of cis-[PtCl2(CO)(PPh3)] toward SnCl2·2H2O has been studied with use of acetone, acetonitrile, and chloroform as solvents. In acetone and acetonitrile, ligand rearrangement reactions occur, but in chloroform only the simple insertion of SnCl2 into one Pt-Cl bond is observed. Similar solvent effects are observed in the reactions of [Pt2(μ-Cl)2Cl2(PR3)2] with SnCl2·2H2O, which yield the trans-[PtCl(SnCl3)2(PR3)]- anions in acetone solution but the simple insertion products, [Pt2(μ-Cl)2(SnCl3)2(PR 3)2], in chloroform solution. Reactions of the related complexes cis-[PtCl2(L)(PPh3)] (L = SMe2, C5H5N, p-MeC6H4NH2) with SnCl2·2H2O in acetone solution also occur via ligand rearrangements. 1H, 31P{1H}, and 119Sn{1H} NMR methods, utilizing 13C-labeled carbon monoxide as a probe of geometry, have been employed to assign solution structures and to monitor reaction pathways.
Role of the trichlorostannyl ligand in homogeneous catalysis. 4. Correlations of solution structure with catalytic activity in cis -[PtCl2(L)(PR3)]/SnCl2·2H2O and [Pt2(μ-Cl)2Cl2(PR3) 2]/SnCl2·2H2O (L = PR3, CO, thioether, amine; R = aryl, alkyl)
Anderson, Gordon K.,Billard, Claude,Clark, Howard C.,Davies, Julian A.,Wong, Chun S.
, p. 439 - 443 (2008/10/08)
The catalytic activities of cis-[PtCl2(L)(PR3)]/SnCl2·2H 2O systems in olefin hydrogenation (L = SR′2, p-XC6H4NH2; R = aryl) and olefin hydroformylation (L = CO, R = aryl, alkyl) are discussed. Comparison of cis-[PtCl2(L)(PR3)] with cis-[PtCl2L2] and cis-[PtCl2(PR3)2] shows that the first is the most effective catalyst precursor in the presence of tin(II) chloride. In the light of previous NMR studies on the reactions of these complexes with SnCl2·2H2O, the catalytic results are discussed and the roles of the PR3 group, the ligand, L, the solvent, and SnCl2·2H2O are described. The catalytic activities of [Pt2(μ-Cl)2Cl2(PR3) 2]/SnCl2·2H2O systems are found to be very similar to those for mononuclear systems, particularly where the same catalyst precursor can be easily generated from the dinuclear species. Not surprisingly, the dinuclear systems show a greater solvent dependence arising from the ability of a given solvent to facilitate catalyst rearrangement processes.
Role of the trichlorostannyl ligand in homogeneous catalysis. 2. Spectroscopic studies of the reaction of cis-[PtCl2(CO)(PR3)] with SnCl2·2H2O: Ligand rearrangement reactions in the formation of an olefin hydroformylation catalyst precursor
Anderson, Gordon K.,Clark, Howard C.,Davies, Julian A.
, p. 427 - 433 (2008/10/08)
The complex cis-[PtCl2(CO)(PPh3)] reacts with SnCl2·2H2O in acetone to yield solutions that are active in the catalytic hydroformylation of olefins. Studies by 13{1H}, 31P{1H}, 119Sn{1H}, and 195Pt NMR spectroscopy, including experiments utilizing 13C-labeled carbon monoxide, have shown that cis-[PtCl2(CO)(PPh3)] reacts with SnCl2·2H2O via a ligand rearrangement process. A cationic complex, trans-[PtCl(CO)(PPh3)2]+, and four anionic complexes, three of which are identified as [Pt(SnCl3)5]3-, trans-[PtCl(SnCl3)2(CO)]-, and trans-[PtCl(SnCl3)2(PPh3)]-, are formed. One minor anionic product remains unidentified. Similar chemistry occurs with the analogous P(p-MeC6H4)3 and P(p-FC6H4)3 complexes, but the rearrangement reaction occurs much more slowly with the basic PEt3 ligand. Some conclusions concerning the mechanism of the reaction are presented; SnCl2·2H2O not only serves as a source of SnCl2 moieties, which undergo insertion reactions, but also generates secondary cationic species, which maintain electroneutrality in the system. Attempted isolation of the ionic species leads to a further rearrangement reaction, ultimately yielding cis-[PtCl2(PPh3)2] as the only isolable product.
