Search results for "Protonolysis"
showing 4 items of 4 documents
Amino-phosphanes in Rh(I)-catalyzed hydroformylation: new mechanistic insights using D2O as deuterium-labeling agent
2005
International audience; In previous work, we have demonstrated that the dangling amino group in amino-phosphane ligands increases the rate of Rh-catalyzed styrene hydroformylation as a function of the amino group basicity and of the distance between the P and N functions. We now report additional stereochemical and mechanistic insights resulting from new catalytic experiments performed with Rh-α-P,N catalytic systems in the presence of D2O. In addition to the expected D0 product, the formation of the β-D1 aldehyde, PhCH(CH2D)CHO was observed in all cases by 1H and 13C NMR spectroscopy, indicating that H/D exchange occurs for the rhodium-hydride complex. Minor amounts of a β-D2 product, PhCH…
Synthesis and structure of a new organometallic polyoxomolybdate,
2004
Abstract Acidic aqueous solutions of the [Cp*MoO2(H2O)x]+ ion yield single crystals of the novel organometallic polyoxomolybdate Cp 2 ∗ Mo 6 O 17 via a slow protonolysis of the Mo–Cp* bond. This compound has subsequently been obtained selectively and in good yields from the combination of Cp 2 ∗ Mo 2 O 5 and four equivalents of MoO 4 2 - under acidic conditions. The X-ray structure of Cp 2 ∗ Mo 6 O 17 is analogous to other hexanuclear polyoxometallate ions but is the most distorted so far reported according to the continuous symmetry measure, the inner (μ6-O)Mo6 core featuring a large displacement of the central oxygen atom toward the organometallic moieties and away from the inorganic ones.
Role of Halide Ion in the Mechanism of Protonolysis of the Pt-C Bond in Pt(II) Alkyl and Aryl Complexes.
1985
Abstract A mechanistic study is described for the electrophilic cleavage of the Pt C σ bond in complexes cis -[PtPh 2 (PEtPh 2 ) 2 ] and trans -[PtXR(PEt 3 ) 2 ] (X = Cl and Br, R = Me, Et, n-Pr, n-Bu, CH 2 Ph) by the proton in the presence of halide ions in aqueous methanol (MeOH/H 2 O, 91v/v) which yields cis -[PtClPh(PEtPh 2 ) 2 ] and trans -[PtX 2 (PEt 3 ) 2 ], respectively. The reactions are first-order in substrate for both systems and the general bivariate rate law k obs = [H + ]{ k H + k x K [[X − ]}/(1 + K [[X − ]) is obeyed. The proposed mechanism involves a fast pre-equilibrium formation (K) of a platinum(II) anionic intermediate via interaction of the halide with the square-plan…
Rare-earth metal bis(tetramethylaluminate) complexes supported by a sterically crowded triazenido ligand
2010
Complexes [NNN]Ln(AlMe(4))(2) (Ln = Y, La, Nd, Lu) bearing the sterically demanding aryl-substituted triazenido ligand [(Tph)(2)N(3)] (Tph = [2-(2,4,6-iPr(3)C(6)H(2))C(6)H(4)]) can be obtained from homoleptic complexes Ln(AlMe(4))(3) in moderate yields, both via protonolysis with [(Tph)(2)N(3)]H and a salt metathesis reaction pathway utilizing [(Tph)(2)N(3)]K. In the solid state the Y and Lu derivatives are isostructural, with both tetramethylaluminate groups coordinated in an eta(2) fashion, while one of the [AlMe(4)] ligands of the Nd derivative features a distorted eta(2) coordination mode. Due to the high affinity of the triazenido ligand toward the more Lewis-acidic and harder aluminiu…