97295-81-3Relevant academic research and scientific papers
Syntesis and Reactivity od (dppe)Pt(OMe)2
Bryndza, Henry E.,Kretchmar, Suzanne A.,Tulip, Thomas H.
, p. 977 - 978 (1985)
Synthesis of (dppe)Pt(OMe)2 (1) by NaOMe metathesis on the analogous dichloride is reported along with the thermal and carbonylation chemistry of (1); the release of dimethyl carbonate and dimethyl oxalate from th
Synthesis and reactivity of diphosphino Pt(II) silanolate complexes as molecular models of the interaction of platinum particles with silica
Banditelli, Guido,Pizzotti, Maddalena,Bandini, Anna Laura,Zucchi, Claudia
, p. 72 - 81 (2008/10/08)
A series of di- and monosubstituted cis-platinum(II) silanolate complexes, Pt(OSiR3)2(dppe) (R=Et, 1; R=Me, 2) and Pt(OSiR3)Cl(dppe) (R=Et, 3; R=iPr, 4) where dppe is 1,2-bis(diphenylphosphino)ethane, have been isolated and characterised spectroscopically. Complex 1 does not react with CO and H2 under anhydrous conditions, but the complexes Pt{C(O)OCH3)}2(dppe) (6) and Pt(CO3)(dppe) (7) have been isolated bubbling CO in methanol and CO2 in moist benzene solutions of 1, respectively. The behaviour of 1 towards water or methanol is discussed on the basis of 1H, and 31P{1H} NMR spectroscopic data. The new complex Pt{S2C(OSiEt3)2}(dppe) (8) has been isolated by reaction of 1 with CS2 in benzene solution. This reactivity would suggest a high sensitivity towards water, but not towards H2 or CO, of the bonding of slightly oxidised platinum particles with silanol groups of silica surface. 2002 Elsevier Science B.V. All rights reserved.
β-Hydride Elimination from Methoxo vs. Ethyl Ligands: Thermolysis of (DPPE)Pt(OCH3)2, (DPPE)Pt(CH2CH3)(OCH3) and (DPPE)Pt(CH2CH3)2
Bryndza, Henry E.,Calabrese, Joseph C.,Marsi, Marianne,Roe, D. Christopher,Tam, Wilson,Bercaw, John E.
, p. 4805 - 4813 (2007/10/02)
Thermolysis of (DPPE)Pt(OCH3)2 (1) (DPPE=1,2-bis(diphenylphosphino)ethane, (C6H5)2PCH2CH2P(C6H5)2) at 25 deg C leads to a mixture of methanol, formaldehyde oligomers, and small amounts of carbon monoxide (CO).Kinetics experiments, labeling studies, and solvent effects suggest this decomposition proceeds by initial preequilibrium β-hydride migration to the metal followed by rate-limiting release of organic products.While 1 decomposes at 25 deg C and (DPPE)Pt(CH2CH3)2 only slowly releases ethylene and ethane at 160 deg C, (DPPE)Pt(CH2CH3)(OCH3) (3) decomposes to a mixture of ethylene, ethane, methanol, and formaldehyde oligomers at 100 deg C.The predominance of ethylene over ethane suggests thermolysis proceeding by β-elimination from the ethyl ligand is energetically easier than the comparable process from the methoxo ligand by 0.3 kcal/mol.Labeling studies confirm the preequilibrium nature of this β-elimination.The relative M-C vs.M-O bond strengths are discussed in light of this information.
