Combining Donor Strength and Oxidative Stability in Scorpionates: A Strongly Donating Fluorinated Mesoionic Tris(imidazol-5-ylidene)borate Ligand.

Strongly donating scorpionate ligands support the study of high-valent transition metal chemistry; however, their use is frequently limited by oxidative degradation. To address this concern, we report the synthesis of a tris(imidazol-5-ylidene)borate ligand featuring trifluoromethyl groups surrounding its coordination pocket. This ligand represents the first example of a chelating poly(imidazol-5-ylidene) mesoionic carbene ligand, a scaffold that is expected to be extremely donating. The {NiNO}10 complex of this ligand, as well as that of a previously reported strongly donating tris(imidazol-2-ylidene)borate, has been synthesized and characterized. This new ligand's strong donor properties, as measured by the υNO of its {NiNO}10 complex and natural bonding orbital second-order perturbative energy analysis, are at par with those of the well-studied alkyl-substituted tris(imidazol-2-ylidene)borates, which are known to effectively stabilize high-valent intermediates. The good donor properties of this ligand, despite the electron-withdrawing trifluoromethyl substituents, arise from the strongly donating imidazol-5-ylidene mesoionic carbene arms. These donor properties, when combined with the robustness of trifluoromethyl groups toward oxidative decomposition, suggest this ligand scaffold will be a useful platform in the study of oxidizing high-valent transition-metal species.

A checklist of the bees (Hymenoptera: Apoidea) of Minnesota.

Research studies and conservation actions aimed at improving conditions for bees require a basic understanding of which species are present in a given region. The US state of Minnesota occupies a unique geographic position at the confluence of eastern deciduous forests, northern boreal forests, and western tallgrass prairie, which has led to a diverse and unique bee fauna. In recent years there have been multiple ongoing bee-focused inventory and research projects in Minnesota. Combined with the historic specimens housed in the University of Minnesota Insect Collection and other regional collections, these furnished a wealth of specimens available to form the basis of a statewide checklist. Here, we present the first comprehensive checklist of Minnesota bee species, documenting a total of 508 species in 45 genera. County-level occurrence data is included for each species, and further information on distribution and rarity is included for species of regional or national interest. Some species have their taxonomy clarified, with Perdita citrinella Graenicher, 1910 syn. nov. recognized as a junior synonym of Perdita perpallida Cockerell, 1901, P. bequaerti syn. nov. recognized as a junior synonym of P. pallidipennis Graenicher, 1910 stat. nov., Anthidiellum boreale (Robertson, 1902) stat. nov. recognized as a full species, and Anthidiellium beijingense Portman & Ascher nom. nov. is proposed for A. boreale Wu to resolve the homonymy with A. boreale (Robertson). We further include a list of species that may occur in Minnesota and highlight 11 species occurring in the state that are considered non-native. Recent collecting efforts, as well as increased taxonomic attention paid to Minnesota bees, have resulted in 66 species that have only been documented in the last 10 years. As a first step in determining native bees of conservation concern, we document 38 species that have not been detected in the state during the last 50 years and discuss their conservation status, along with other species for which evidence of decline exists. The checklist of Minnesota bees will continue to grow and change with additional surveys and research studies. In particular, recent surveys have continued to detect new bee species, and many bee groups are in need of taxonomic revision, with the most recent revisions for many genera occurring decades ago. Overall, this checklist strengthens our understanding of the bees of Minnesota and the broader region, informs conservation assessments, and establishes a baseline for faunal change.

Individual bee foragers are less-efficient transporters of pollen for plants from which they collect the most pollen in their scopae.

PREMISE: Bees provision most of the pollen removed from anthers to their larvae and transport only a small proportion to stigmas, which can negatively affect plant fitness. Though most bee species collect pollen from multiple plant species, we know little about how the efficiency of bees' pollen transport varies among host plant species or how it relates to other aspects of generalist bee foraging behavior that benefit plant fitness, such as specialization on individual foraging bouts. METHODS: We compared the pollen collected and transported by three bee species for 46 co-occurring plant species. Specifically, we compared the relative abundance of pollen taxa in the individual bees' scopae, structures where bees store pollen to provision larvae, with the relative abundance of pollen taxa on the rest of bees' bodies, which is more likely to be transferred to stigmas. RESULTS: Bees carried five times more pollen grains in their scopae than elsewhere on their bodies. Within foraging bouts, bees were relatively specialized in their pollen collection, but transported proportionally less pollen for the host plants on which they specialized. Across foraging bouts, two bee species transported proportionally less pollen for some of their host plants than for others, though differences didn't consistently follow the same trend as at the foraging bout scale. CONCLUSIONS: Our results suggest that foraging-bout specialization, which is known to reduce heterospecific pollen transfer, also results in less-efficient pollen transport. Thus, bee foragers that visit predominantly one plant species may have contrasting effects on that plant's fitness.

Rare and declining bee species are key to consistent pollination of wildflowers and crops across large spatial scales.

Biodiversity promotes ecosystem function (EF) in experiments, but it remains uncertain how biodiversity loss affects function in larger-scale natural ecosystems. In these natural ecosystems, rare and declining species are more likely to be lost, and function needs to be maintained across space and time. Here, we explore the importance of rare and declining bee species to the pollination of three wildflowers and three crops using large-scale (72 sites across 5000 km2 ), multi-year datasets. Half of the sampled bee species (82/164) were rare or declining, but these species provided only ~15% of overall pollination. To determine the number of species important to EF, we used two methods of "scaling up," both of which have previously been used for biodiversity-function analysis. First, we summed bee species' contributions to pollination across space and time and then found the minimum set of species needed to provide a threshold level of function across all sites; according to this method, effectively no rare and declining bee species were important to pollination. Second, we account for the "insurance value" of biodiversity by finding the minimum set of bee species needed to simultaneously provide a threshold level of function at each site in each year. The second method leads to the conclusion that 25 rare and eight declining bee species (36% and 53% of all rare and declining bee species, respectively) are included in the minimum set. Our findings provide some of the strongest evidence yet that rare and declining species are key to meeting threshold levels of EF, thereby providing a more direct link between real-world biodiversity loss and EF.

Two, Three, or Not to Be? Elucidating Multiple Bonding in d6 Pseudotetrahedral Oxo and Imide Complexes.

Late-transition-metal oxo and imide complexes play an important role in the catalytic functionalization and activation of small molecules. An emerging theme in this area over the past few decades has been the use of lower coordination numbers, and pseudotetrahedral geometries in particular, to stabilize what would otherwise be highly reactive species. However, the bonding structure in d6 oxo and imide complexes in this geometry is ambiguous. These species are typically depicted with a triple bond; however, recent experimental evidence suggests significant empirical differences between these complexes and other triply bonded complexes with lower d counts. Here we use a suite of computational orbital localization methods and electron density analyses to probe the bonding structure of isoelectronic d6 CoIII oxo and imide complexes. These analyses suggest that a triple-bond description is inaccurate because of a dramatically weakened σ interaction. While the exact bond order in these cases is necessarily dependent on the model used, several metrics suggest that the strength of the metal-O/N bond is most similar to that of other formally doubly bonded complexes.