Chloride, Alkoxide, or Silicon: The Bridging Ligand Dictates the Spin State in Dicobalt Expanded Pincer Complexes

Bienenmann, Roel L. M.; Asundi, Arun S.; Lutz, Martin; Sarangi, Ritimukta; Broere, Daniël L. J.

doi:10.1021/acs.organomet.4c00374

Title: Chloride, Alkoxide, or Silicon: The Bridging Ligand Dictates the Spin State in Dicobalt Expanded Pincer Complexes

Journal Article · Wed Nov 27 00:00:00 UTC 2024 · Organometallics

DOI: https://doi.org/10.1021/acs.organomet.4c00374 · OSTI ID:2500257

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^[2]; Lutz, Martin ^[1];

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Utrecht University (The Netherlands)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

We report the synthesis and characterization of a series of high- and low-spin dicobalt complexes of the ^tBuPNNP expanded pincer ligand. Reacting this dinucleating ligand in its neutral form with two equiv of CoCl₂(tetrahydrofuran)_1.5 yields a high-spin dicobalt complex featuring one Co inside and one Co outside of the dinucleating pocket. Performing the same reaction in the presence of two equivalents of KOtBu provides access to a high-spin dicobalt complex wherein both Co centers are bound within the PNNP pocket, and this complex also features a bridging OtBu ligand. Reacting either of the high-spin complexes with excess diethyl silane affords a low-spin dicobalt complex containing two unusual bridging Si-based ligands. These complexes were investigated using NMR spectroscopy, XAS, single crystal X-ray structure determination, and computational methods, showing that the Si-based ligands are best described as base-stabilized silylenes.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Universiteit Utrecht (The Netherlands)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2500257

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 1 Vol. 44; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Chloride, Alkoxide, or Silicon: The Bridging Ligand Dictates the Spin State in Dicobalt Expanded Pincer Complexes

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