An Azide-Free Synthesis of Metallodiazomethanes Using Nitrous Oxide.

Diazo compounds are valuable reagents in synthesis but usually require the use of potentially explosive or toxic starting materials. Here, we report the synthesis and isolation of alkali metal diazomethanides by the reaction of metalated ylides with nitrous oxide, resulting in a formal exchange of the phosphine ligand by dinitrogen. The reaction proceeds through a Wittig-like mechanism via a [3 + 2] cycloaddition of N2O across the ylide bond with release of phosphine oxide. The metalated diazomethanes exhibit an increased thermal stability due to the stronger binding of N2 compared to neutral diazomethanes. This is reflected in short C-N distances and red-shifted N-N vibrations and enables versatile applications such as for the preparation of transition metal diazomethanide complexes and the synthesis of 1,2,3-triazoles from nitriles, diazoacetates from carbon dioxide, or alkynes from aldehydes.

P,N-Coordinating Ylide-Functionalized Phosphines (NYPhos): A Ligand Platform for the Selective Monoarylation of Small Nucleophiles.

Palladium-catalyzed coupling reactions of small nucleophiles are of great interest, but challenging due to difficulties in selectivity control. Herein, we report the development of a new platform of P,N-ligands consisting of ylide-functionalized phosphines with aminophosphonium groups (NYPhos) to address this challenge. These phosphine ligands are easily accessible in a wide structural diversity with highly modular electronic and steric properties. Based on a family of 14 ligands the selective monoarylation of acetone as well as other challenging ketones and amides was accomplished with record-setting activities even for aryl chlorides at room temperature including late-stage functionalizations of drug molecules. Moreover, ammonia and other small primary amines could be coupled at mild conditions. Isolation and structure analyses of palladium complexes within the catalytic cycle confirmed that the P,N-coordination mode is necessary to achieve the observed selectivities. It also demonstrated the facile adjustability of the N-donor strength, which is beneficial for the targeted design of tailored P,N-ligands for future applications.

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents.

How different is carbon compared to other elements in the periodic table? Can carbon compounds be regarded as coordination complexes with carbon as the central element undergoing a facile exchange of its ligands? Although carbon clearly plays a special role among the elements of the periodic table, recent studies have drawn parallels between the bonding situation and the reactivity of carbon compounds to transition metal complexes. This Perspective summarizes recent reports about ylidic and zwitterionic compounds that were shown to exhibit ambiguous bonding situations that can be interpreted as donor-acceptor interactions similar to the bond between a metal and a neutral ligand. Based on this conception, ligand exchange reactions prototypical of transition metal complexes were realized at carbon atoms, enabling new synthetic strategies for the synthesis of reactive species and building blocks. In particular, the exchange of N2, CO, and phosphine ligands led to the development of a mild method for accessing new compounds and reagents with unusual properties, such as vinylidene ketenes or stable ketenyl anions, that open up a diverse but still poorly explored follow-up chemistry.

The Cyanoketenyl Anion [NC3O].

Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for more complex molecules but tend to isomerize or cyclize and therefore are difficult to isolate. Using a mild ligand exchange reaction at the carbon in α-metalated ylides, we have now succeeded in the synthesis and gram-scale isolation of the elusive cyanoketenyl anion [NC3O]-. Despite its assumed cumulene-like structure and the delocalization of the negative charge across the whole 5-atom molecule, it features a bent geometry with a nucleophilic central carbon atom. Computational studies reveal an ambiguous bonding situation in the anion, which can be illustrated only by a combination of different resonance structures. Nonetheless, the anion features remarkable stability, thus allowing the storage of its potassium-crown ether salt and its application as a highly functional synthetic building block. The cyanoketenyl anion readily reacts with a series of small molecules to form more complex organic compounds, including industrially valuable compounds such as cyanoacetate. This work demonstrated that reactive species can be generated by novel synthesis methods and open up atom-economic pathways to complex compounds from small abundant molecules.

Phosphinoyl-Substituted Ketenyl Anions: Synthesis and Substituent Effects on the Structural Properties.

Ketenyl anions are versatile intermediates in synthetic chemistry and have recently become accessible as isolable reagents from metalated ylides by exchange of the phosphine with CO. Herein, we report on a systematic study of substituent effects on the structure and bonding situation in ketenyl anions. A series of phosphinoyl-substituted ketenyl anions {[R2P(X)CCO]- with X = O, NTol, S, Se} were prepared by carbonylation of the corresponding yldiides and isolated as their corresponding potassium salts. NMR and IR spectroscopic analyses together with computational studies demonstrate that the more electron-withdrawing oxo- and iminophosphinoyl substituents increase the s-character in the bond to the ketene moiety and hence the ynolate character of the anion. This trend is particularly seen in solution, whereas the solid-state properties are influenced by packing effects affecting the bonding situation.

Selectivity Control of the Ligand Exchange at Carbon in α-Metallated Ylides as a Route to Ketenyl Anions.

α-Metallated ylides have recently been reported to undergo phosphine by CO exchange at the ylidic carbon atom to form isolable ketenyl anions. Systematic studies on the tosyl-substituted yldiides, R3 P=C(M)Ts (M=Li, Na, K), now reveal that carbonylation may lead to a competing metal salt (MTs) elimination. This side-reaction can be controlled by the choice of phosphine, metal cation, solvent and co-ligands, thus enabling the selective isolation of the ketenyl anion [Ts-CCO]M (2-M). Complexation of 2-Na by crown ether or cryptand allowed structure elucidation of the first free ketenyl anion [Ts-CCO]- , which showed an almost linear Ts-C-C linkage indicative for a pronounced ynolate character. However, DFT studies support a high charge at the ketenyl carbon atom, which is reflected in the selective carbon-centered reactivity. Overall, the present study provides important information on the selectivity control of ketenyl anion formation which will be crucial for future applications.

Inverting the Electronic Structure of Diylidylgermylenes by Backbone Modification.

Owing to the strong electron-donating ability of ylide substituents, diylidyltetrylenes are usually highly nucleophilic species with strong donor capacities. Here, we demonstrate that their electronic properties are in fact highly flexible and can be effectively tuned through variation of the substituent in the ylide backbone. Initial density functional theory studies showed that cyano groups are particularly capable in lowering the LUMO energy of diylidyl germylenes thus turning these usually highly nucleophilic species into electrophilic compounds. This was confirmed by experimental studies. Attempts to synthesize the germylene (YCN )2 Ge [with YCN =Ph3 P-(C)-CN] from the corresponding metalated ylide YCN K selectively led to germanide [(YCN )3 Ge)K]2 thus reflecting the electrophilic nature of the intermediate formed germylene. XRD analysis of single crystals of (YCN )2 Ge - serendipitously obtained through protonative cleavage of one ylide from the germanide - revealed a monomeric structure with rather long Ge-ylide linkages, which corroborates well with a pure single bond and no stabilization of the empty pπ orbital at germanium through π bonding. The germanide exhibits methanide-like reactivity towards chalcogens but a likewise weak Ge-C bond as demonstrated by the insertion of carbon dioxide.

Transition metal-free ketene formation from carbon monoxide through isolable ketenyl anions.

The capacity of transition metals to bind and transform carbon monoxide (CO) is critical to its use in many chemical processes as a sustainable, inexpensive C1 building block. By contrast, only few s- and p-block element compounds bind and activate CO, and conversion of CO into useful carbonyl-containing organic compounds in such cases remains elusive. We report that metalated phosphorus ylides provide facile access to ketenyl anions ([RC=C=O]-) by phosphine displacement with CO. These anions are very stable and storable reagents with a distinctive electronic structure between that of the prototypical ketene (H2C=C=O) and that of ethynol (HC≡C-OH). Nonetheless, the ketenyl anions selectively react with a range of electrophiles at the carbon atom, thus offering high-yielding and versatile access to ketenes and related compounds.

Ylide-Stabilized Phosphenium Cations: Impact of the Substitution Pattern on the Coordination Chemistry.

Although N-heterocyclic phosphenium (NHP) cations have received considerable research interest due to their application in organocatalysis, including asymmetric synthesis, phosphenium cations with other substitution patterns have hardly been explored. Herein, the preparation of a series of ylide-substituted cations of type [YPR]+ (with Y=Ph3 PC(Ph), R=Ph, Cy or Y) and their structural and coordination properties are reported. Although the diylide-substituted cation forms spontaneous from the chlorophosphine precursor, the monoylidylphosphenium ions required the addition of a halide-abstraction reagent. The molecular structures of the cations reflected the different degrees of electron donation from the ylide to the phosphorus center depending on the second substituent. Molecular orbital analysis confirmed the stronger donor properties of the ylide systems compared to NHPs with the mono-ylide substituted cations featuring a more pronounced electrophilicity. This was mirrored by the reaction of the cations towards gold chloride, in which only the diylide-substituted cation [Y2 P]+ formed the expected LAuCl]+ complex, while the monoylide-substituted compounds reacted to the chlorophosphine ligands by transfer of the chloride from gold to the phosphorus center. These results demonstrate the tunability of ylide-functionalized phosphorus cations, which should allow for further applications in coordination chemistry in the future.

Catalytic Hydrodefluorination of C-F Bonds by an Air-Stable PIII Lewis Acid.

Catalytic hydrodefluorination (HDF) of unactivated fluoroalkanes or CF3 -substituted aryl species is performed using the PIII Lewis acids, [(bipy)PPh]2+ (12+ ) and [(terpy)PPh]2+ (22+ ) under mild conditions (25 or 50 °C). Mechanistic studies indicate that activation of C-F bond by the PIII center is key. Particularly noteworthy is that the catalyst 2[B(C6 F5 )4 ]2 is air-stable and readily accessible from bench-stable, commercially available reagents in one-step and can be used without isolation.