The importance of understanding (pre)catalyst activation in versatile C-H bond functionalisations catalysed by [Mn2(CO)10].

Mn-catalysed reactions offer great potential in synthetic organic and organometallic chemistry and the success of Mn carbonyl complexes as (pre)catalysts hinges on their stabilisation by strong field ligands enabling Mn(i)-based, redox neutral, catalytic cycles. The mechanistic processes underpinning the activation of the ubiquitous Mn(0) (pre)catalyst [Mn2(CO)10] in C-H bond functionalisation reactions is now reported for the first time. By combining time-resolved infra-red (TRIR) spectroscopy on a ps-ms timescale and in operando studies using in situ infra-red spectroscopy, insight into the microscopic bond activation processes which lead to the catalytic activity of [Mn2(CO)10] has been gained. Using an exemplar system, based on the annulation between an imine, 1, and Ph2C2, 2, TRIR spectroscopy enabled the key intermediate [Mn2(CO)9(1)], formed by CO loss from [Mn2(CO)10], to be identified. In operando studies demonstrate that [Mn2(CO)9(1)] is also formed from [Mn2(CO)10] under the catalytic conditions and is converted into a mononuclear manganacycle, [Mn(CO)4(C^N)] (C^N = cyclometallated imine), a second molecule of 1 acts as the oxidant which is, in turn, reduced to an amine. As [Mn(CO)4(C^N)] complexes are catalytically competent, a direct route from [Mn2(CO)10] into the Mn(i) catalytic reaction coordinate has been determined. Critically, the mechanistic differences between [Mn2(CO)10] and Mn(i) (pre)catalysts have been delineated, informing future catalyst screening studies.

Gold(III), Mercury(II), and Palladium(II) Complexes of a Series of Isomeric Bis(mono- and dialkoxyphenyl)pyridines: Introduction of Gold through Transmetalation and Catalysis.

A series of isomeric bis-2,6-(monoalkoxyphenyl)pyridine and bis-2,6-(dialkoxyphenyl)pyridine ligands were synthesized and characterized. In order to prepare their chlorogold(III) complexes, intermediate chloromercury(II) complexes were first prepared, but unlike observations from previous studies where they were obtained impure and at best in moderate yield, here pure complexes were synthesized, many in rather high yields. Depending on the substitution pattern of the alkoxy chains on the ligands, mono- and/or dimercurated complexes were obtained, characterized by 1H, 13C{1H}, and 199Hg NMR spectroscopy as well as, in several cases, by X-ray crystallography. Factors that may explain this unusual reactivity are discussed. In most cases, transmetalation to the related chlorogold(III) complex proceeded smoothly, although lower yields were obtained when starting from doubly mercurated precursors. Prompted by the propensity of these ligands to mercurate, attempts were made to effect direct auration, but none was successful. However, dimeric, orthometalated complexes of palladium(II) could be prepared and were also amenable to transmetalation to the chlorogold(III) complex, providing for a mercury-free synthesis.

A Modular Strategy for the Synthesis of Macrocycles and Medium-Sized Rings via Cyclization/Ring Expansion Cascade Reactions.

Macrocycles and medium-sized rings are important in many scientific fields and technologies but are hard to make using current methods, especially on a large scale. Outlined herein is a strategy by which functionalized macrocycles and medium-sized rings can be prepared using cyclization/ring expansion (CRE) cascade reactions, without resorting to high dilution conditions. CRE cascade reactions are designed to operate exclusively via kinetically favorable 5-7-membered ring cyclization steps; this means that the problems typically associated with classical end-to-end macrocyclization reactions are avoided. A modular synthetic approach has been developed to facilitate the simple assembly of the requisite linear precursors, which can then be converted into an extremely broad range of functionalized macrocycles and medium-sized rings using one of nine CRE protocols.

Metal-Mediated Catalytic Polarization Transfer from para Hydrogen to 3,5-Dihalogenated Pyridines.

The neutral catalysts [IrCl(H)2(NHC)(substrate)2] or [IrCl(H)2(NHC)(substrate)(sulfoxide)] are used to transfer polarization from para hydrogen (pH2) to 3,5-dichloropyridine and 3,5-dibromopyridine substrates. This is achieved in a rapid, reversible, and low-cost process that relies on ligand exchange within the active catalyst. Notably, the sulfoxide-containing catalyst systems produced NMR signal enhancements between 1 and 2 orders of magnitude larger than its unmodified counterpart. Consequently, this signal amplification by reversible exchange hyperpolarization method can boost the 1H, 13C, and 15N nuclear magnetic resonance (NMR) signal intensities by factors up to 4350, 1550, and 46,600, respectively (14.0, 1.3, and 15.4% polarization). In this paper, NMR and X-ray crystallography are used to map the evolution of catalytically important species and provide mechanistic rational for catalytic efficiency. Furthermore, applications in spontaneous radiofrequency amplification by stimulated emission and NMR reaction monitoring are also shown.

Coumarin C-H Functionalization by Mn(I) Carbonyls: Mechanistic Insight by Ultra-Fast IR Spectroscopic Analysis.

Mn(I) C-H functionalization of coumarins provides a versatile and practical method for the rapid assembly of fused polycyclic pyridinium-containing coumarins in a regioselective manner. The synthetic strategy enables application of bench-stable organomanganese reagents in both photochemical- and thermal-promoted reactions. The cyclomanganated intermediates, and global reaction system, provide an ideal testing ground for structural characterization of the active Mn(I) carbonyl-containing species, including transient species observable by ultra-fast time-resolved spectroscopic methods. The thermodynamic reductive elimination product, solely encountered from reaction between alkynes and air-stable organometallic cyclomanganated coumarins, has enabled characterization of a critical seven-membered Mn(I) intermediate, detected by time-resolved infrared spectroscopy, enabling the elucidation of the temporal profile of key steps in the reductive elimination pathway. Quantitative data are provided. Manganated polycyclic products are readily decomplexed by AgBF4 , opening-up an efficient route to the formation of π-extended hybrid coumarin-pyridinium compounds.

Enhancing the Air Stability of Dimolybdenum Paddlewheel Complexes: Redox Tuning through Fluorine Substituents.

The optical and electrochemical properties of quadruply bonded dimolybdenum paddlewheel complexes (Mo2PWCs) make them ideal candidates for incorporation into functional materials or devices, but one of the greatest bottlenecks for this is their poor stability toward atmospheric oxygen. By tuning the potential at which the Mo2 core is oxidized, it was possible to increase the tolerance of Mo2PWCs to air. A series of homoleptic Mo2PWCs bearing fluorinated formamidinate ligands have been synthesized and their electrochemical properties studied. The oxidation potential of the complexes was tuned in a predictable fashion by controlling the positions of the fluorine substituents on the ligands, as guided by a Hammett relationship. Studies into the air stability of the resulting complexes by multinuclear NMR spectroscopy show an increased tolerance to atmospheric oxygen with increasingly electron-withdrawing ligands. The heteroleptic complex Mo2(DFArF)3(OAc) [where DFArF = 3,5-(difluorophenyl)formamidinate] shows remarkable tolerance to oxygen in the solid state and in chloroform solutions. Through the employment of easily accessible ligands, the stability of the Mo2 core toward oxygen has been enhanced, thereby making Mo2PWCs with electron-withdrawing ligands more attractive candidates for the development of functional materials.