Organometallic Gas‐phase Ion Chemistry and Catalysis: Insights Into the Use of Metal Catalysts to Promote Selectivity in the Reactions of Carboxylic Acids and Their Derivatives

Abstract

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Near thermal, selective liberation of hydrogen from formic acid catalysed by copper hydride ate complexes

“…The copper hydride anions [(L)Cu(H)] − (where L = H − , O 2 CH − , BH 4 − and CN − ) were prepared in the gas-phase, following procedures from previous reports, 12,17 via electrospray ionisation multistage mass spectrometry (ESI-MS n ) experiments. 29 1_H , [(H)Cu(H)] − ( m / z 65), and 1_O 2 CH , [(HCO 2 )Cu(H)] − ( m / z 109), were prepared by mass selection of the precursor copper formate ion, [Cu(O 2 CH) 2 ] − ( m / z 153) and subjecting the ion to sequential stages of collision-induced dissociation (CID) (Fig. S1, ESI†).…”

Bringing a Mechanistic Lens to the Development of New Transfer Hydroarylation Isodesmic Reactions for the Synthesis of Amides, Thioamides, Amidines, Alkenes and Ketones from Carboxylic Acids via Extrusion and Insertion Elementary Steps

“…We have employed ion trap mass spectrometers, which can be regarded as "complete chemical laboratories", [69,70] since the resultant organometallic product ions can be isolated and their reactivity (both unimolcular and bimolecular) can be studied, while their structures can be interrogated via gas-phase spectroscopic methods (UV [71,72] or IR [73] ) on suitably modified mass spectrometers. [74][75][76][77] At the same time that we were studying gas-phase decarboxylation of metal carboxylates and the subsequent reactions of the resultant organometallic ions (much of this earlier work has been reviewed [70,78] ), there was a renaissance of condensed phase work on metal catalysed decarboxylative coupling reactions. Some landmarks include Myers' report on the decarboxylative Heck cross-coupling reaction (Scheme 2a) [79,80] and Goossen's decarboxylative biaryl crosscoupling reaction (Scheme 2b).…”

Photooxidation of Isoprene by Titanium Oxide Cluster Anions with Dimensions up to a Nanosize

“…Gas-phase titanium oxide clusters can be used as ideal models of the active sites on titania materials. − The structures and reactivity of small to nanosized titanium oxide clusters have been extensively studied. − The study of the interactions of titanium oxide clusters with CO under dark conditions demonstrated the outstanding reactivity of the titanium oxide clusters with specific compositions ((TiO 2 ) x O – and (TiO 2 ) x + ) that have atomic oxygen radical anions (O •– ) as the active sites. , It has been proposed that (TiO 2 ) x O – clusters with x values of up to 50 still have the O •– radicals . Although there have been many studies on the reactivity of titanium oxide clusters under dark conditions, the photoactivity of these oxide clusters has been almost untouched …”