1361576-52-4Relevant academic research and scientific papers
A remarkably active iron catecholate catalyst immobilized in a porous organic Polymer
Kraft, Steven J.,Sanchez, Raul Hernandez,Hock, Adam S.
, p. 826 - 830 (2013)
A single-site, iron catecholate-containing porous organic polymer was prepared and utilized as a stable and remarkably active catalyst for the hydrosilylation of ketones and aldehydes. In some instances, catalyst loadings of 0.043-2.1 mol % [Fe] were sufficient for complete hydrosilylation of aldehydes and ketones within 15 min at room temperature. The catalyst can be recycled at least three times without a drop in catalytic activity. This system is an example of an immobilized homogeneous catalyst with no homogeneous analogue.
A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies
Ghosh, Chandrani,Mukhopadhyay, Tufan K.,Flores, Marco,Groy, Thomas L.,Trovitch, Ryan J.
supporting information, p. 10398 - 10406 (2015/11/16)
Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, PyEtPDI, allowed preparation of the respective dihalide complex, (PyEtPDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ5-N,N,N,N,N-PyEtPDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = 3/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ5-N,N,N,N,N-PyEtPDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min-1 when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)(nBu)]. The aldehyde hydrosilylation activity observed for (κ5-N,N,N,N,N-PyEtPDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.
Rare-earth metal allyl and hydrido complexes supported by an (NNNN)-type macrocyclic ligand: Synthesis, structure, and reactivity toward biomass-derived furanics
Abinet, Elise,Martin, Daniel,Standfuss, Sabine,Kulinna, Heiko,Spaniol, Thomas P.,Okuda, Jun
experimental part, p. 15014 - 15026 (2012/02/06)
The preparation and characterization of a series of neutral rare-earth metal complexes [Ln(Me3TACD)(η3-C3H 5)2] (Ln=Y, La, Ce, Pr, Nd, Sm) supported by the 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane anion (Me3TACD -) are reported. Upon treatment of the neutral allyl complexes [Ln(Me3TACD)(η3-C3H5) 2] with Bronsted acids, monocationic allyl complexes [Ln(Me3TACD)(η3-C3H5)(thf) 2][B(C6X5)4] (Ln=La, Ce, Nd, X=H, F) were isolated and characterized. Hydrogenolysis gave the hydride complexes [Ln(Me3TACD)H2]n (Ln=Y, n=3; La, n=4; Sm). X-ray crystallography showed the lanthanum hydride to be tetranuclear. Reactivity studies of [Ln(Me3TACD)R2]n (R=η3-C3H5, n=0; R=H, n=3,4) towards furan derivatives includes hydrosilylation and deoxygenation under ring-opening conditions.
