916480-65-4

Upstream product

• 50-00-0 formaldehyd 
• 3188-13-4 ethyl chloromethyl ether 
• 24544-04-5 2,6-diisopropylbenzenamine 

Downstream Products

• 1381848-38-9 [CuCl(IPr^Me)] 
• 848085-29-0 1,3-bis(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazol-3-ium-2-ide 
• 1188360-04-4 1,3-bis(2,6-diisopropylphenyl)-4,5-dimethyl-3-imidazolium-2-carboxylate 

Relevant academic research and scientific papers

Linking Low-Coordinate Ge(II) Centers via Bridging Anionic N-Heterocyclic Olefin Ligands

We introduce a large-scale synthesis of a sterically encumbered N-heterocyclic olefin (NHO) and illustrate the ability of its deprotonated form to act as an anionic four-electron bridging ligand. The resulting multicenter donating ability has been used to link two low oxidation state Ge(II) centers in close proximity, leading to bridging Ge-Cl-Ge and Ge-H-Ge bonding environments supported by Ge2C2 heterocyclic manifolds. Reduction of a dimeric [RGeCl]2 species (R = anionic NHO, [(MeCNDipp)2C=CH]- Dipp = 2,6-iPr2C6H3) did not give the expected acyclic RGeGeR analogue of an alkyne, but rather ligand migration/disproportionation transpired to yield the known diorganogermylene R2Ge and Ge metal. This process was examined computationally, and the ability of the reported anionic NHO to undergo atom migration chemistry contrasts with what is typically found with bulky monoanionic ligands (such as terphenyl ligands).

Synthesis and characterization of IPrMe-containing silver(I), gold(I) and gold(III) complexes

The compounds 4,5-dimethyl-N,N′-bis(2,6-diisopropylphenyl)imidazol-2- ylidene silver chloride [AgCl(IPrMe)] 3 and 4,5-dimethyl-N,N′- bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) chloride [AuCl(IPr Me)] 4 have been synthesized. The attempted synthesis of the corresponding 4,5-dimethyl-N,N′-bis(2,6-diisopropylphenyl)imidazol-2- ylidene gold(III) chloride by oxidative addition of chlorine gas on 4 allowed for the formation of the expected complex, concomitantly with 6, resulting from a chlorination of a methyl group situated in the backbone of the NHC (N-heterocyclic carbene). Additionally, the buried volume %Vbur of the IPrMe ligand in [AgCl(IPrMe)] 3 and [AuCl(IPr Me)] 4 complexes was calculated and compared to %Vbur of more classical NHCs. This quantification of the steric hinderance of the IPrMe ligand reveals the influence of the substituent modulation in the backbone of NHCs.

A more sustainable and efficient access to IMes·HCl and IPr·HCl by ball-milling

Herein is described a mechanochemical one-pot two-step procedure giving access to various NHC (N-heterocyclic carbene) precursors. This original approach enabled the production of the widely used IPr·HCl, IMes·HCl, Io-Tol·HCl and ICy·HCl in much better yields than conventional solvent-based procedures, while the environmental impact was drastically reduced.

NHC Ligands Tailored for Simultaneous Regio- and Enantiocontrol in Nickel-Catalyzed Reductive Couplings

An exceptionally hindered class of enantiopure NHC ligands has been developed. While racemic forms had previously been utilized, a scalable and practical route to the enantiopure form of this ligand class is described utilizing a Buchwald-Hartwig N,N-diarylation in a highly sterically demanding environment. Using this newly accessible ligand class, nickel-catalyzed enantioselective reductive coupling reactions of aldehydes and alkynes have been developed. These studies illustrate that the newly available NHC ligands are well suited for simultaneous control of regio- and enantioselectivity, even in cases with internal alkynes possessing only very subtle steric differences between two aliphatic substituents. The steric demand of the new ligand class enables a complementary regiochemical outcome compared with previously described enantioselective processes. Using this method, a number of allylic alcohol derivatives were efficiently obtained with high regioselectivity (up to >95:5) and high enantioselectivity (up to 94% ee). The reaction conditions can also be extended to the reaction of aldehydes and allenes, providing silyl-protected allylic alcohol derivatives possessing a terminal methylene substituent. Computational studies have explained the origin of the exceptional steric demand of this ligand class, the basis for enantioselectivity, and the cooperative relationship of the aldehyde, alkyne, and ligand in influencing enantioselectivity.

Unraveling the synthesis of homoleptic [Ag(N, N -diaryl-NHC)2]Y (Y = BF4, PF6) complexes by ball-milling

A user-friendly and general mechanochemical method was developed to access rarely described NHC (N-heterocyclic carbene) silver(i) complexes featuring N,N-diarylimidazol(idin)ene ligands and non-coordinating tetrafluoroborate or hexafluorophosphate counter anions. Comparison with syntheses in solution clearly demonstrated the superiority of the ball-milling conditions.