Bisgermylene-Stabilized Stannylone: Catalytic Reduction of Nitrous Oxide and Nitro Compounds via Element-Ligand Cooperativity.

This study describes the synthesis, structural characterization, and catalytic application of a bis(germylene)-stabilized stannylone (2). The reduction of digermylated stannylene (1) with 2.2 equiv of potassium graphite (KC8) leads to the formation of stannylone 2 as a green solid in 78% yield. Computational studies showed that stannylone 2 possesses a formal Sn(0) center and a delocalized 3-c-2-e π-bond in the Ge2Sn core, which arises from back-donation of the p-type lone pair electrons on the Sn atom to the vacant orbitals of the Ge atoms. Stannylone 2 can serve as an efficient precatalyst for the selective reduction of nitrous oxide (N2O) and nitroarenes (ArNO2) with the formation of dinitrogen (N2) and hydrazines (ArNH-NHAr), respectively. Exposure of 2 with N2O (1 atm) resulted in the insertion of two oxygen atoms into the Ge-Ge and Ge-Sn bonds, yielding the germyl(oxyl)stannylene (3). Moreover, the stoichiometric reaction of 2 with 1-chloro-4-nitrobenzene afforded an amido(oxyl)stannylene (4) through the complete scission of the N-O bonds of the nitroarene. Stannylenes 3 and 4 serve as catalytically active species for the catalytic reduction of nitrous oxide and nitroarenes, respectively. Mechanistic studies reveal that the cooperation of the low-valent Ge and Sn centers allows for multiple electron transfers to cleave the N-O bonds of N2O and ArNO2. This approach presents a new strategy for catalyzing the deoxygenation of N2O and ArNO2 using a zerovalent tin compound.

Double 1,2-Carbon Migration at Mixed Heavier Sn=Ge Vinylidenes.

1,2-migration is one recurring isomerization reaction in organic chemistry. In contrast, double 1,2-migration remains rare and limited to transition-metal complexes. Herein, we describe the synthesis, characterization and reactivity of mixed heavier Sn=Ge vinylidenes. Double 1,2-carbon migration enables the isomerization of the stannagermenylidene (3) to the germastannenylidene (4). X-ray diffraction analysis and DFT calculations revealed that 3 and 4 feature a Sn=Ge double bond. The reaction of 3 with IMe4 (1,3,4,5-tetramethylimidazoline-2-ylidene) results in the electron redistribution in the Sn=Ge core to give the germylone-stannylene adduct (5). Moreover, treatment of 3 with 0.25 equiv. of (AlCp*)4 produces the heteronuclear aluminyl stannagermyne (6).

A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene.

Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Herein, we report the synthesis of a silylene-stabilized ditin(0) complex (2) by reduction of a silylene-supported dibromostannylene (1) with 1 equivalent of magnesium (I) dimer in toluene. The structure of 2 was established by single crystal X-ray diffraction analysis. Density Functional Theory calculations revealed that complex 2 bears a Sn=Sn double bond and one lone pair of electrons on each of the Sn(0) atoms. Remarkably, complex 2 is readily methylated to give a mixed-valent methylditin cation (4), which undergoes topomerization in solution though a reversible 1,2-Me migration along a Sn=Sn bond. Computational studies showed that the three-coordinate Sn atom in 4 is the dominant electrophilic center, and allows for facile reaction with KHBBus3 furnishing an unprecedented N-heterocyclic silylenes-stabilized distannavinylidene (5). The synthesis of 2, 4 and 5 demonstrates the exceptional ability of N-heterocyclic silylenes to stabilize low valent tin complexes.

Mechanism and Origin of Site Selectivity and Regioselectivity of Scandium-Catalyzed Benzylic C-H Alkylation of Tertiary Anilines with Alkenes.

Benzylic C(sp3)-H alkylation of tertiary anilines with alkenes by an anilido-oxazoline-ligated scandium alkyl catalyst was recently reported with C-H site selectivity and alkene-dependent regioselectivity. Revealing the mechanism and origin of selectivity is undoubtedly of great importance for understanding experimental observations and developing new reactions. Herein, density functional theory (DFT) calculations have been carried out on the model reaction of Sc-catalyzed benzylic C(sp3)-H alkylation of N,N-dimethyl-o-toluidine with allylbenzene. The reaction generally undergoes the generation of active species, alkene insertion, and protonation steps. The difference of the distortion energy of the aniline moiety in transition states, which is related to the ring size of the forming metallacycles, accounts for the site selectivity of C-H activation. Benzylic C(sp3)-H activation possessing less strained five-membered metallacycle compared to the ortho-C(sp2)-H and α-methyl C(sp3)-H activation results in benzylic C(sp3)-H alkylation observed experimentally. Both steric and electronic factors are responsible for the 1,2-insertion regioselectivity for alkyl-substituted alkenes, while electronic factors control the 2,1-insertion manner for vinylsilanes. The analysis of original alkene substrates further strengthens the understanding of the alkene-dependent regioselectivity. These results help us to obtain the mechanistic understanding and are expected to be conducive to the development of new C-H functionalization reactions.

Bifunctional Lewis Base Catalyzed Asymmetric N-Allylic Alkylation of 2-Hydroxypyridines.

A chiral Lewis base catalyzed enantioselective N-allylic alkylation of 2-hydroxypyridines and MBH carbonates is documented, affording a convenient access to N-alkylated 2-pyridones with up to 99% ee and 99% yield. Experimental and computational studies have revealed that the strong hydrogen bond interaction between the chiral Lewis base catalyst and 2-hydroxypyridines plays a crucial role in this reaction for the reactivity, chemoselectivity, and enantioselectivity.

Substrate Facilitating Roles in Rare-Earth-Catalyzed C-H Alkenylation of Pyridines with Allenes: Mechanism and Origins of Regio- and Stereoselectivity.

Although considerable progress has been achieved in C-H functionalization by cationic rare-earth alkyl complexes, the potential facilitating roles of heteroatom-containing substrates during the catalytic cycle remain highly underestimated. Herein, theoretical studies on the model reaction of C(sp2)-H addition of pyridines to allenes by scandium catalyst were carefully carried out to reveal the detailed mechanism. A coordinating pyridine substrate as a ligand can effectively stabilize some key structures. An obvious facilitating role delivered by the coordinating pyridine was found for allene insertion, while the pyridine-free mechanism prefers to occur for C(sp2)-H activation processes. Importantly, the elusive role of heteroatom-containing substrates was systematically revealed for the C-H activation event by designing a metal/ligand combination of catalysts and substrates. We found that the pyridyl C(sp2)-H activation would be switched to the pyridine-coordinated mechanism in the cases of the designed Y and La catalysts. To date, this is the first time to realize the potential substrate-facilitating role in cationic rare-earth-catalyzed C-H activation processes. Moreover, theoretical predictions show that similar switchable mechanisms also work for other types of C-H bonds and other heteroatom-involved substrates by fine-adjusting the steric surroundings of catalysts. The two C-H activation mechanisms are mainly the result of the delicate balance between electronic and steric factors. In general, the catalytic system with less steric hindrance prefers to undergo the substrate-coordinated mechanism. In contrast, the substrate-free mechanism is favorable due to steric repulsion. These results are helpful for us to better understand the variant mechanisms in rare-earth-catalyzed C-H functionalization at the atomistic level and may help guide the rational design of new catalytic reactions. In addition, the origins of the regio- and stereoselectivity were discussed through geometric parameters and distortion/interaction analysis.

Mechanistic insights into rare-earth-catalysed C-H alkylation of sulfides: sulfide facilitating alkene insertion and beyond.

The catalytic C-H alkylation with alkenes is of much interest and importance, as it offers a 100% atom efficient route for C-C bond construction. In the past decade, great progress in rare-earth catalysed C-H alkylation of various heteroatom-containing substrates with alkenes has been made. However, whether or how a heteroatom-containing substrate would influence the coordination or insertion of an alkene at the catalyst metal center remained elusive. In this work, the mechanism of Sc-catalysed C-H alkylation of sulfides with alkenes and dienes has been carefully examined by DFT calculations, which revealed that the alkene insertion could proceed via a sulfide-facilitated mechanism. It has been found that a similar mechanism may also work for the C-H alkylation of other heteroatom-containing substrates such as pyridine and anisole. Moreover, the substrate-facilitated alkene insertion mechanism and a substrate-free one could be switched by fine-tuning the sterics of catalysts and substrates. This work provides new insights into the role of heteroatom-containing substrates in alkene-insertion-involved reactions, and may help guide designing new catalysis systems.