UCSD-CNRS Joint Research Chemistry Laboratory

Mass‐independent isotopic signatures for δ 33 S, δ 34 S, and δ 36 S produced in the photolysis of sulfur dioxide exhibit a strong wavelength dependence. Photolysis experiments with three light sources (ArF excimer laser (193 nm), mercury resonance lamp (184.9 and 253.7 nm), and KrF excimer laser (248 nm)) are presented. Products of sulfur dioxide photolysis undertaken with 193‐nm radiation exhibit characteristics that are similar to sulfur multiple‐isotope data for terrestrial sedimentary rock samples older than 2450 Ma (reported by Farquhar et al. [2000a]), while photolysis experiments undertaken with radiation at other wavelengths (longer than 220 nm and at 184.9 nm) exhibit different characteristics. The spectral window between 190 and 220 nm falls between the Schumann‐Runge bands of oxygen and the Hartley bands of ozone, and its absorption is therefore more sensitive to changes in altitude and atmospheric oxygen content than neighboring wavelengths. These two observations are used to suggest a link between sulfur dioxide photolysis at 193 nm and sulfur isotope anomalies in Archean rocks. This hypothesis includes the suggestion that UV wavelengths shorter than 200 nm penetrated deep in the Earth's atmosphere during the Archean. Potential implications of this hypothesis for the chemistry, composition, and UV absorption of the atmosphere are explored. We also explore the implications of these observations for documentation of bacterial sulfur metabolisms early in Earth's history.

The MURANO trial (A Study to Evaluate the Benefit of Venetoclax Plus Rituximab Compared With Bendamustine Plus Rituximab in Participants With Relapsed or Refractory Chronic Lymphocytic Leukemia [CLL]; ClinicalTrials.gov identifier #NCT02005471) reported superior progression-free survival (PFS) and overall survival (OS) with venetoclax-rituximab (VenR) vs bendamustine-rituximab (BR) in relapsed/refractory (R/R) CLL. Patients were randomized to 2 years of VenR (n = 194; rituximab for the first 6 months) or 6 months of BR (n = 195). Although undetectable minimal residual disease (uMRD) was achieved more often with VenR, the long-term implications of uMRD with this fixed-duration, chemotherapy-free regimen have not been explored. We report MRD kinetics and updated outcomes with 5 years' follow-up. Survival benefits with VenR vs BR were sustained (median PFS [95% confidence interval]: 53.6 [48.4, 57.0] vs 17.0 [15.5, 21.7] months, respectively, P < .0001; 5-year OS [95% confidence interval]: 82.1% [76.4, 87.8] vs 62.2% [54.8, 69.6], P < .0001). VenR was superior to BR, regardless of cytogenetic category. VenR-treated patients with uMRD at end of treatment (EOT; n = 83) had superior OS vs those with high-MRD+ (n = 12): 3-year post-EOT survival rates were 95.3% vs 72.9% (P = .039). In those with uMRD at EOT, median time to MRD conversion was 19.4 months. Of 47 patients with documented MRD conversion, 19 developed progressive disease (PD); median time from conversion to PD was 25.2 months. A population-based logistic growth model indicated slower MRD median doubling time post-EOT with VenR (93 days) vs BR (53 days; P = 1.2 × 10-7). No new safety signals were identified. Sustained survival, uMRD benefits, and durable responses support 2-year fixed-duration VenR treatment in R/R CLL.

Classical N-heterocyclic carbenes (NHCs), such as thiazolylidenes, 1,2,4-triazolylidenes, and imidazol(in)-2-ylidenes, are powerful organocatalysts for aldehyde transformations through the so-called Breslow intermediates (BIs). The reactions usually occur via electron-pair-transfer processes. In contrast, the use of BIs in single-electron transfer (SET) pathways is still in its infancy, and the scope is limited by the moderate reduction potential of BIs derived from classical NHCs (ca. −1.0 V versus standard calomel electrode [SCE]). Here, we report that BIs from 1,2,3-triazolylidenes, a type of mesoionic carbene (MIC), have a reduction potential as negative as −1.93 V versus SCE and thus are among the most potent organic reducing agents reported to date. They are reductive enough to undergo SET with iodoarenes, which allows the highly efficient inter- and intramolecular MIC-catalyzed arylacylation of styrenes and alkenes, respectively.

Quantum chemical calculations using density functional theory have been carried out for the cyclic (alkyl)(amino)carbene (cAAC) complexes of the group 11 atoms [TM(cAAC)2] (TM = Cu, Ag, Au) and their cations [TM(cAAC)2](+). The nature of the metal-ligand bonding was investigated with the charge and energy decomposition analysis EDA-NOCV. The calculations show that the TM-C bonds in the charged adducts [TM(cAAC)2](+) are significantly longer than in the neutral complexes [TM(cAAC)2], but the cations have much higher bond dissociation energies than the neutral molecules. The intrinsic interaction energies ΔEint in [TM(cAAC)2](+) take place between TM(+) in the (1)S electronic ground state and (cAAC)2. In contrast, the metal-ligand interactions in [TM(cAAC)2] involve the TM atoms in the excited (1)P state yielding strong TM p(π) → (cAAC)2 π backdonation, which is absent in the cations. The calculations suggest that the cAAC ligands in [TM(cAAC)2] are stronger π acceptors than σ donors. The trends of the intrinsic interaction energies and the bond dissociation energies of the metal-ligand bonds in [TM(cAAC)2] and [TM(cAAC)2](+) give the order Au > Cu > Ag. Calculations at the nonrelativistic level give weaker TM-C bonds, particularly for the gold complexes. The trend for the bond strength in the neutral and charged adducts without relativistic effects becomes Cu > Ag > Au. The EDA-NOCV calculations suggest that the weaker bonds at the nonrelativistic level are mainly due to stronger Pauli repulsion and weaker orbital interactions. The NBO picture of the C-TM-C bonding situation does not correctly represent the nature of the metal-ligand interactions in [TM(cAAC)2].

Two (cAAC)2Cu complexes, featuring a two-coordinate copper atom in the formal oxidation state zero, were prepared by reducing (Et2-cAAC)2Cu(+)I(-) with metallic sodium in THF, and by a one-pot synthesis using Me2-cAAC, Cu(II)Cl2, and KC8 in toluene in a molar ratio of 2:1:2, respectively. Both complexes are highly air and moisture sensitive but can be stored in the solid state for a month at room temperature. DFT calculations showed that in these complexes the copper center has a d(10) electronic configuration and the unpaired electron is delocalized over two carbene carbon atoms. This was further confirmed by the EPR spectra, which exhibit multiple hyperfine lines due to the coupling of the unpaired electron with (63,65)Cu isotopes, (14)N, and (1)H nuclei.

Transition metal complexes featuring a metal-nitrogen multiple bond have been widely studied due to their implication in dinitrogen fixation and catalytic nitrogen-carbon bond formation. Terminal copper- and silver-nitrene complexes have long been proposed to be the key intermediates in aziridination and amination reactions using azides as the nitrogen source. However, due to their high reactivity, these species have eluded isolation and spectroscopic characterization even at low temperatures. In this paper we report that a stable phosphinonitrene reacts with coinage metal trifluoromethanesulfonates, affording bridging and terminal copper- and silver-nitrene complexes, which are characterized by NMR spectroscopy and single crystal X-ray diffraction analysis.

Cationic phosphoranimines have been postulated as intermediates in phosphazene polymerization chemistry. However, the high electrophilicity of the phosphorus center has so far prevented their characterization. Here, we report the synthesis of two Lewis base-free iminophosphonium salts, obtained by reaction of a stable phosphinonitrene with methyl trifluoromethanesulfonate and trifluoromethanesulfonic acid. These cationic species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Using 4-(dimethylamino)pyridine, a corresponding Lewis-base adduct has also been isolated.

The popularity of NHCs in transition metal catalysis has prompted the development of chiral versions as electron-rich neutral stereodirecting ancillary ligands for enantioselective transformations. Herein we demonstrate that cyclic (alkyl)(amino)carbene (CAAC) ligands can also engage in asymmetric transformations, thereby expanding the toolbox of available chiral carbenes.

Photolysis of [bis(dicyclohexylamino)phosphanyl](trimethylsilyl)diazomethane leads to the corresponding stable carbene1b, which reacts with triethylborane affording a borane–carbene adduct2b, characterized by spectroscopy in solution before rearrangement and fragmentation into P-dicyclohexylamino-C-(ethyl)(trimethylsilyl)phosphaalkene3b; trimethylsilyltrifluoromethanesulfonate adds to 1b giving the methylenephosphonium4b.

N-heterocyclic carbenes, such as imidazole-2-ylidenes and imidazolin-2-ylidenes, the popular class of singlet carbenes introduced by Arduengo in 1991 have not been shown to be ambiphilic owing to the two σ-withdrawing, π-donating amino groups flanking the carbene centre. However, our experimental data suggest that ring-expanded N-heterocyclic carbenes (RE-NHCs), especially the seven and eight membered rings, are significantly ambiphilic. Our results also show that the steric environment in RE-NHCs can become a determining factor for controlling the E-H bond activation.

The coordination of Ge9 Zintl clusters at (carbene)CuI moieties is explored, and the complexes [(CAAC)Cu]2[η3-Ge9{Si(TMS)3}2] (1), (CAAC)Cu[η3-Ge9{Si(TMS)3}3] (2), and (MIC)Cu[η3-Ge9{Si(TMS)3}3] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1–3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge9R2]2– and [Ge9R3]− [R = Si(TMS)3] cluster ligands, respectively, and yields complexes of (carbene)CuI (carbene = CAAC, MIC) moieties exhibiting η3-coordination modes of the Ge9 deltahedron to the Cu atom. In 1, [Ge9R2]2– acts as a η3-bridging unit for two (CAAC)CuI moieties, and 2 and 3 feature single (carbene)CuI (CAAC and MIC) fragments η3-connected to [Ge9R3]− units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge3 triangular faces for all (carbene)CuIGe9 complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [1H, 13C{1H}, and 29Si{1H}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge9 clusters with carbene ligands at CuI atoms.

The first Z -stereoselective catechodithiolate ruthenium complexes containing achiral and chiral cyclic(alkyl)(amino)carbene ligands are reported.

Diapycnal mixing shapes the distribution of climatically-important tracers, such as heat and carbon, as these are carried by dense water masses in the ocean interior. Here, we analyze a suite of observation-based estimates of diapycnal mixing to assess its role within the Atlantic Meridional Overturning Circulation. The rate of water mass transformation in the Atlantic Ocean’s interior shows that there is a robust buoyancy increase in the North Atlantic Deep Water (NADW), with a diapycnal circulation of up to 4 Sv between 24N and 32S in the Atlantic Ocean. Moreover, tracers within the southward-flowing NADW may undergo a substantial diapycnal transfer, equivalent to hundreds of metres in the vertical. This result is confirmed with a zonally-averaged numerical model of the AMOC and indicates that tracer mixing can lead to divergent global pathways and ventilation timescales following the upwelling of tracers in the Southern Ocean. These results point to the need for a realistic mixing representation in climate models in order to understand and credibly project the ongoing climate change.

N-Heterocyclic carbene (NHC) ligands possess the ability to stabilize metal-based nanomaterials for a broad range of applications. With respect to metal–hydride nanomaterials, however, carbenes are rare, which is surprising if one considers the importance of metal–hydride bonds across the chemical sciences. In this study, we introduce a bottom-up approach leveraging preexisting metal–metal m-center-n-electron (mc-ne) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper–hydride nanocluster, [(CAAC)6Cu14H12][OTf]2. Using electrochemical measurements and thermogravimetric analysis we showcase that this cluster exhibits superior stability compared to Stryker’s reagent, a popular commercial phosphine-based copper hydride catalyst. Density Functional Theory (DFT) calculations reveal that the enhanced stability stems from hydride-to-ligand backbonding with the π-accepting carbene. This new cluster emerges as a highly efficient and selective copper–hydride pre-catalyst across six reaction classes, thereby providing a bench-stable alternative for catalytic applications.

Cyclic(alkyl)(amino)carbene (CAAC) ligands are found to perturb regioselectivity of the copper-catalyzed carboboration of terminal alkynes, favoring the less commonly observed internal alkenylboron regiosomer through an α-selective borylcupration step. A variety of carbon electrophiles participate in the reaction, including allyl alcohols derivatives and alkyl halides. The method provides a straightforward and selective route to versatile tri-substituted alkenylboron compounds that are otherwise challenging to access.

A novel class of well-defined rhodium and iridium complexes containing various chiral cyclic(alkyl)(amino)carbene (ChiCAAC) ligands has been synthesised and fully characterized. While no enantioselectivity was observed with chiral Rh-CAAC, the Ir-CAAC counterparts demonstrated good performances in the asymmetric hydrogenation of various allylic alcohols and derivatives with up to 86% ee. Mechanistic studies, including deuteration experiments revealed that the reduction proceeds via direct alkene hydrogenation rather than via isomerization.