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Methods for the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels that are both efficient and economically viable could greatly enhance global security and prosperity. Currently, the major route to convert natural gas and coal to liquids is Fischer-Tropsch catalysis, which is potentially applicable to any source of(More)
While the addition of C-H bonds to three-coordinate Ir(I) fragments is a central theme in the field of C-H bond activation, addition to square planar four-coordinate complexes is far less precedented. The dearth of such reactions may be attributed, at least in part, to kinetic factors elucidated in seminal work by Hoffmann. C-H additions to square planar(More)
A pincer-ligated iridium complex, (PCP)Ir (PCP = κ(3)-C6H3-2,6-[CH2P(t-Bu)2]2), is found to undergo oxidative addition of C(sp(3))-O bonds of methyl esters (CH3-O2CR'), methyl tosylate (CH3-OTs), and certain electron-poor methyl aryl ethers (CH3-OAr). DFT calculations and mechanistic studies indicate that the reactions proceed via oxidative addition of C-H(More)
Tandem dehydrogenation-olefin-metathesis catalyst systems, comprising a pincer-ligated iridium-based alkane dehydrogenation catalyst and a molybdenum-based olefin-metathesis catalyst, are reported to effect the metathesis-cyclooligomerization of cyclooctane and cyclodecane to give cycloalkanes with various carbon numbers, predominantly multiples of the(More)
Synthesis and characterization of new (PONOP) [2,6-bis(di-tert-butylphosphinito)pyridine] metal (Ni, Pd, Pt) complexes are reported. Surprisingly, these compounds [(PONOP)MCl]Cl in the presence of 1 equiv of superhydride (LiEt(3)BH) formed a new class of complexes (H-PONOP)MCl, in which the pyridine ring in the PONOP ligand lost its aromaticity as a result(More)
Catalytic activities of a series of functional bipyridine-based Ru(II) complexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional Ru(II) complex (3 a) bearing 6,6'-dihydroxy-2,2'-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1(More)
Carbon-fluorine bonds are the strongest known single bonds to carbon and as a consequence can prove very hard to cleave. Alhough vinyl and aryl C-F bonds can undergo oxidative addition to transition metal complexes, this reaction has appeared inoperable with aliphatic substrates. We report the addition of C(sp(3))-F bonds (including alkyl-F) to an iridium(More)
Evidence for key σ-complex intermediates in the hydrogenolysis of the iridium-methyl bond of (PONOP)Ir(H)(Me)(+) (1) [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] has been obtained. The initially formed η(2)-H(2) complex, 2, was directly observed upon treatment of 1 with H(2), and evidence for reversible formation of a σ-methane complex, 5, was(More)
The atom economical borrowing hydrogen methodology enables the use of alcohols as alkylating agents for selective C-C bond formation. A bifunctional 2-(2-pyridyl-2-ol)-1,10-phenanthroline (phenpy-OH) based Ru(ii) complex (2) was found to be a highly efficient catalyst for the one-pot β-alkylation of secondary alcohols with primary alcohols and double(More)
Considerable differences in reactivity and selectivity for 2-hydroxypyridine (2-HP) derived ruthenium complexes in transfer hydrogenation are described. Bifunctional Ru(ii)-(phenpy-OH) [phenpy-OH: 2-(2-pyridyl-2-ol)-1,10-phenanthroline] complex () exhibited excellent catalytic activity in transfer hydrogenation (TH) of ketones and nitriles. Notably, in(More)