A novel efficient biphasic tandem catalytic process (biTCP) with a high carbon efficiency was developed for synthesizing cycloalkanes that can used to make dense jet fuels from renewable terpenoid biomass (such as 1,8-cineole).
Aqueous‐phase organometallic chemistry is an important yet still underexplored area of chemistry and catalysis. An important aspect of organometallic chemistry in water is the potential to utilize the benefits of homogeneous catalysis (selectivity, activity, etc.) and couple that with the benefits of heterogeneous catalysis (ease of separation). Organometallic complexes can be made soluble in water through the use of various water‐soluble ligands. An overview of the unique characteristics of water with respect to organometallic complexes and reactivity are discussed including pH effects, hydrogen bonding, salt effects, and metal‐carbon bond stability. An introduction to the various types of ligands utilized in water‐soluble organometallic chemistry is provided. The most prevalent water‐soluble ligands are phosphines designed with polar or hydrophilic functional groups. Amines, ammonium salts, functionalized NHCs, and derivatives of cyclopentadiene or arenes are some of the other ligands that have been utilized in aqueous‐phase organometallic chemistry and catalysis. Water also makes a good ligand for some water‐soluble organometallic complexes and the reactivity of coordinated water can play a significant role in reactivity and/or catalysis. An introduction to the behavior of metal hydride ligands in aqueous environments is also presented. Finally, selected catalytic reactions carried out in aqueous media are discussed including hydrogenation, hydration, CC bond forming reactions, oxidation, hydroformylation, and olefin metathesis.
RuCl 2 (PTA) 4 (PTA = 1,3,5-triaza-7-phosphaadamantane) is an active, recyclable, air-stable,a queous-phase nitrile hydration catalyst. The development of an in situ generated aqueous-phase nitrileh ydration catalyst (RuCl 3 ·3 H 2 O + 6equivalents PTA) is reported.T he activity of the in situ catalyst is comparable to RuCl 2 (PTA) 4 .T he effects of [PTA] on the activity of the reaction were investigated:t he catalytic activity, in general, increases as the pH goes up, which shows ap ositive correlation with [PTA].T he pH effectsw ere furthere xplored for both the in situ and RuCl 2 (PTA) 4 cata-lyzed reactioni np hosphate buffer solutionsw ith particular attention given to pH 6.8 buffer.I ncreased catalytic activity was observed at pH 6.8 versus waterf or both systems with turnover frequency (TOF) up to 135 h À1 observed for RuCl 2 (PTA) 4 and 64 h À1 for the in situ catalyst. Catalystl oading down to 0.001 mol %w as examinedw ith turnover numbers as high as 22 000 reported. Similar to the preformed catalyst, RuCl 2 (PTA) 4 ,t he in situ catalyst could be recycled more than five times withouts ignificant loss of activity from eitherw ater or pH 6.8 buffer. Results and DiscussionThe relatively simple synthesis [34,35] and high activity of RuCl 2 (PTA) 4 as ac atalystf or the hydration of nitrilesp rompted us to investigate utilizingRuCl 3 and PTAasaninsitu generated [a] Dr.
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