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Organometallics Distinguished Author Symposium in honor of Robert Gilliard:
02:00pm - 04:30pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Professor Paul J Chirik, Organizer; Ian Tonks, Presider
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid
Division/Committee: [INOR] Division of Inorganic Chemistry
Monday
Introductory Remarks
02:00pm - 02:05pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid

Monday
3638435 - Multifaceted reactivity of boron-based vertices in polyhedral boron clusters
02:05pm - 02:40pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid
This talk is dedicated to the celebration of Prof. Robert Gilliard’s contributions to the main group inorganic chemistry on the occasion of his 2021 Organometallics Distinguished Author Award. My presentation will focus on the aspects of fundamental chemistry associated with the functionalization and properties of polyhedral boron clusters. Specifically, we have been interested in the generation and reactivity studies of B-centered nucleophiles and radicals associated with these species. During the first half of the talk, I will describe how the nucleophilic and/or radical character of the boron vertices in some of these clusters can be harnessed by using late transition metal chemistry. These observations have guided our development of several synthetic methodologies enabling derivatization of these species in a catalytic fashion via pathways that are reminiscent of cross-coupling chemistry with classical organic substrates. Furthermore, we have recently successfully applied this strategy for bioconjugation transformations with unprotected peptides and proteins. In the second half of the presentation, I will demonstrate how some boron clusters can act as competent nucleophiles without the aid of transition metals. I will highlight some unique features of the nucleophilic character of the small boron clusters that can be applied to carbon-based electrophiles as well as main-group electrophiles (e.g., R2PCl, RSeCl) to generate the corresponding borylated species featuring B-C, B-Se and B-P bonding interactions.
Monday
3657680 - Molecular metal chalcogenide clusters inspired by CoMoS: The role of metal-support interactions in tuning reactivity at a single edge site
02:40pm - 03:15pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid
A family of molecular M/Co/Se metal chalcogenide clusters inspired by CoMoS catalysts were prepared with a single, well-defined active site M = Cr, Mn, Fe, Co, Cu and Zn. The role of the electronic metal-support interaction between the active site and the support is investigated with respect to the emerging electronic structure and catalytic activity, and a structure-activity relationship is constructed. The experimental foray into the geometry, electronic structure, magnetic properties, and reactivity of the nanoclusters is complemented by DFT studies.
Monday
3656980 - Super-oxidized iron nitrido and super-reduced iron nitrosyl complexes in tris-carbene coordination spheres
03:15pm - 03:50pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Karsten Meyer, Presenter
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid
Iron nitrido [(TIMMNmes)Fe(N)]n+ (n = 1 to 3) and iron nitrosyl [(TIMENmes)Fe(NO)]n (n = 3+ to 1–) complexes with the sterically encumbered, N-anchored tris-N-heterocyclic carbene chelates tris-[2-(3-mesityl-imidazol-2-ylidene)alkyl]amine (alkyl: methyl = TIMMN; ethyl = TIMEN) were synthesized and characterized by various spectroscopic, magneto- and electrochemical techniques, including single-crystal X-ray diffractometry. Supported by computational analyses, this study provides comprehensive insights into the electronic and molecular structures of an unprecedented series of iron nitrosyls and nitrides in very similar coordination environments but with wide variety of oxidation states; including a stable Fe(VI) complex in tetragonal symmetry. Progress towards the synthesis of an Fe(VII) complex is presented.
Ligand Tailoring Towards Iron Nitrido and Nitrosyl Complexes in Chelating tris-Carbene Ligand Environments

Ligand Tailoring Towards Iron Nitrido and Nitrosyl Complexes in Chelating tris-Carbene Ligand Environments


Monday
3650941 - Synthesis and photophysics of π-conjugated luminescent phosphorus and nitrogen compounds
03:50pm - 04:25pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
John Protasiewicz, Presenter
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid
2-R-1,3-benzoxaphospholes (R-BOPs) and 2-R-1,3-benzazaphospholes (R-BAPs) are rare examples of low coordinate phosphorus compounds that display photoluminescence (PL). We have been working to prepare new related molecules having greater extension of their π-systems and to integrate these building blocks into extended materials having increasing conjugation and added functionality. We have recently discovered that isolable carbenes can react reversibly with luminescent materials to modulate the emission of these materials, as well as found unusual reactions with palladium and platinum complexes. Our latest work on these new materials, as well as their characterization by X-ray crystallography, and UV-visible spectroscopy, and fluorescence measurements, will be discussed.

Monday
Concluding Remarks
04:25pm - 04:30pm USA / Canada - Pacific - March 21, 2022 | Location: Room 7A (San Diego Convention Center)
Division: [INOR] Division of Inorganic Chemistry
Session Type: Oral - Hybrid