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Abstract The incorporation of cationic groups onto electron‐poor compounds is a viable strategy for achieving potent electron acceptors, as evidenced by reports of air‐stable radical forms of large aromatic diimides such as naphthalene and perylene diimides. These ions have also been observed to exhibit anion–π interaction tendencies of interest in molecular recognition applications. The benefits of phosphonium incorporation, however, have not yet been extended to the smallest benzene diimides. Here, we report that dibrominated pyromellitic diimide and mellophanic diimide both readily undergo substitution reactions with phosphine sources to yield bisphosphonium compounds. In the single crystalline form, these dications display anion‐π interactions and, in the case of mellophanic diimide, the stabilization of a bromide–water H−bonding ring pattern. The reaction of these dications with chemical reductants readily provides the singly and doubly reduced redox states, which were characterized by UV‐vis spectroscopy and found to exhibit intense absorptions extending into the near‐IR region. Taken together, this work demonstrates that phosphonium incorporation onto congested aromatic diimide scaffolds is synthetically viable and produces unusual electron‐poor compounds. 

International Ocean Discovery Program Expedition 359 was designed to address changes in sea level and currents, along with monsoon evolution in the Indian Ocean. The Maldives archipelago holds a unique and mostly unread Indian Ocean archive of the evolving Cenozoic icehouse world. Cores from eight drill sites in the Inner Sea of the Maldives provide the tropical marine record that is key for better understanding the effects of this global evolution in the Indo-Pacific realm. In addition, the bank geometries of the carbonate archipelago provide a physical record of changing sea level and ocean currents. The bank growth occurs in pulses of aggradation and progradation that are controlled by sea level fluctuations during the early and middle Miocene, including the mid-Miocene Climate Optimum. A dramatic shift in development of the carbonate edifice from a sea level–controlled to a predominantly current-controlled system appears to be directly linked to the evolving Indian monsoon. This phase led to a twofold configuration of bank development: bank growth continued in some parts of the edifice, whereas in other places, banks drowned. Drowning steps seem to coincide with onset and intensification of the monsoon-related current system and subsequent deposition of contourite fans and large-scale sediment drifts. As such, the drift deposits will provide a continuous record of Indian monsoon development in the region of the Maldives. A major focus of Expedition 359 was to date precisely the onset of the current system. This goal was successfully completed during the expedition. The second important outcome of Expedition 359 was groundtruthing the hypothesis that the dramatic, pronounced change in style of the carbonate platform sequence stacking was caused by a combination of relative sea level fluctuations and ocean current system changes. These questions are directly addressed by the shipboard scientific data. In addition, Expedition 359 cores will provide a complete Neogene δ13C record of the platform and platform margin sediments and a comparison with pelagic records over the same time period. This comparison will allow assessment of the extent to which platform carbonates record changes in the global carbon cycle and whether changes in the carbon isotopic composition of organic and inorganic components covary and the implications this has on the deep-time record. This determination is important because such records are the only type that exists in deep time. 

Abstract Formal nickelate(−I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e⁻complexes were synthesized by one‐electron reduction of the corresponding Ni⁰→M^IIIprecursors, and were investigated by single‐crystal X‐ray diffraction, EPR spectroscopy, and quantum chemical calculations. Collectively, the experimental and computational data support: 1) the strengthening of the Ni−M bond upon one‐electron reduction, and 2) the delocalization of the unpaired spin across the Ni and M atoms. An intriguing electronic configuration is revealed where three valence electrons occupy two σ‐type bonding interactions: Ni(3d)²→M and σ‐(Ni−M)¹. The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4p_zand M np_z/ns atomic orbitals. 

Abstract Oxoiron(IV) units are often implicated as intermediates in the catalytic cycles of non‐heme iron oxygenases and oxidases. The most reactive synthetic analogues of these intermediates are supported by tetradentate tripodal ligands withN‐methylbenzimidazole or quinoline donors, but their instability precludes structural characterization. Herein we report crystal structures of two [Fe^IV(O)(L)]²⁺complexes supported by pentadentate ligands incorporating these heterocycles, which show longer average Fe–N distances than the complex with only pyridine donors. These longer distances correlate linearly with log k₂′ values for O‐ and H‐atom transfer rates, suggesting that weakening the ligand field increases the electrophilicity of the Fe=O center. The sterically bulkier quinoline donors are also found to tilt the Fe=O unit away from a linear N‐Fe=O arrangement by 10°.