Tracking the Process of a Solvothermal Domino Reaction Leading to a Stable Triheteroarylmethyl Radical: A Combined Crystallographic and Mass‐Spectrometric Study

Abstract

A new free carbon radical was obtained in a microwave‐assisted solvothermal reaction of the primary amine (1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)methanamine with FeCl3⋅6 H2O in methanol at 140 °C. Through a combination of crystallography and electrospray ionization mass spectrometry, the reaction process was studied. The longest domino reaction includes 14 steps and forms up to 12 new covalent bonds (9 C−N and 3 C−C bonds) and 3 five‐membered heterocycles. For the first time, the homolytic cleavage of a C−O bond was used to synthesize a triarylmethyl radical.

In Situ Metal‐Assisted Ligand Modification Induces Mn4 Cluster‐to‐Cluster Transformation: A Crystallography, Mass Spectrometry, and DFT Study

“…[7,21] To furtherc onfirm the occurrence of the transformation,w e performed ESI-MS on reactionp recipitatesf rom different times. [ 4,6,8,10, and 12 h, respectively,a nd then decreased (Figure 3). The times at which[ Mn 4 L x L' 6Àx ]i ncrease to their peak valuesr eveal an obvious order and time-dependent nature.I ti ndicates that [Mn 4 L x L' 6Àx ]i ntermediate fragments first form and then decompose.O ur attempts to crystallize the intermediate fragments came to nothing, which is also consistent with the amorphous nature seen by PXRD.…”

“…[1][2][3][4] Although hydro/solvothermal synthesis has often been considered as black magic due to the scant information that is available on the reactionp rocesses, the use of ESI-MSi sp rovingq uite valuable in deciphering the intermediates. [5][6][7][8] Witha dditional informationas af unction of reaction time and calculation of the energetics by DFT,e videncei sb eing collected that allows one to understand the intricate process and eventually deduce a mechanism. [9,10] Application of ESI-MS and crystallography, backed up by DFTc alculations, has been successfully applied to study severald ifferent kinds of coordination clusters, for example, polyoxometalates,c oordination polyhedra, and 3d-metal coordinationc lusters.…”

“…To understand how chemical reactions progress while identifying the intermediates so that schemes and mechanisms can be drawn is one of the basic goals in chemistry . Although hydro/solvothermal synthesis has often been considered as black magic due to the scant information that is available on the reaction processes, the use of ESI‐MS is proving quite valuable in deciphering the intermediates . With additional information as a function of reaction time and calculation of the energetics by DFT, evidence is being collected that allows one to understand the intricate process and eventually deduce a mechanism .…”

Temperature‐induced formation of two dinuclear dysprosium complexes with different magnetic properties

“…The structure of an organic ligand usually does not change during the formation of a complex with a specific connection and topological structure via coordination among the organic ligand, coordinating anion and metal ion . In recent years, hydrothermal/solvothermal technology has gradually become an important synthetic means, and a directional construction of new organic frameworks, coordination polymers and coordination molecular clusters has been achieved . Under solvothermal conditions, owing to the effects of temperature and pressure, certain metal ions with strong catalytic ability can further catalyze the reaction of the starting ligand by coordinating under in situ conditions, which will produce several organic compounds that are difficult to build via traditional organic synthesis .…”

“…In addition, the newly produced ligands can further participate in the assembly to form metal complexes with novel structures and excellent physical and chemical properties . Therefore, solvothermal in situ metal/ligand reactions are called bridges between inorganic and organic reactions . While additional examples of organic ligands involved in coordination during the formation of complexes have been found, these examples are mostly involved in the formation of 3d metal complexes .…”