Four-Coordinate Co(III) Imide with an Unusually Tilted Terminal Imido Ligand
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ABSTRACT:
SUBMITTER: Gu L
PROVIDER: S-EPMC10865434 | biostudies-literature | 2024 Jan
REPOSITORIES: biostudies-literature
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Project description:Inspired by mechanistic proposals for N2 reduction at the nitrogenase FeMo cofactor, we report herein a new, strongly σ-donating heteroscorpionate ligand featuring two weak-field pyrazoles and an alkyl donor. This ligand supports four-coordinate Fe(I)-N2, Fe(II)-Cl, and Fe(III)-imido complexes, which we have characterized using a variety of spectroscopic and computational methods. Structural and quantum mechanical analysis reveal the nature of the Fe-C bonds to be essentially invariant between the complexes, with conversion between the (formally) low-valent Fe-N2 and high-valent Fe-imido complexes mediated by pyrazole hemilability. This presents a useful strategy for substrate reduction at such low-coordinate centers and suggests a mechanism by which FeMoco might accommodate the binding of both π-acidic and π-basic nitrogenous substrates.
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Project description:The reaction of the cobalt(I) complex [(TIMMNmes )CoI ](BPh4 ) (2) (TIMMNmes =tris-[2-(3-mesitylimidazolin-2-ylidene)methyl]amine) with 1-adamantylazide yields the cobalt(III) imido complex [(TIMMNmes )CoIII (NAd)](BPh4 ) (3) with concomitant release of dinitrogen. The N-anchor in diamagnetic 3 features an unusual, planar tertiary amine, which results from repulsive electrostatic interaction with the filled d(z2 )-orbital of the cobalt ion and negative hyperconjugation with the neighboring methylene groups. One-electron oxidation of 3 with [FeCp2 ](OTf) provides access to the rare, high-valent cobalt(IV) imido complex [(TIMMNmes )CoIV (NAd)](OTf)2 (4). Despite a half-life of less than 1 h at room temperature, 4 could be isolated at low temperatures in analytically pure form. Single-crystal X-ray diffractometry and EPR spectroscopy corroborate the molecular structure and the d5 low-spin, S= 1/2 , electron configuration. A computational analysis of 4 suggests high covalency within the CoIV =NAd bond with non-negligible spin density located at the imido moiety, which translates into substantial triplet nitrene character.
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Project description:Multidisciplinary applications of four-coordinate boron(III) complexes make them very attractive and challenging research field in chemistry, biology and material sciences. The dual role played by boron atom in stabilising the chelate ligand and enhancing the π-conjugation makes them very useful as luminescent materials for organic electronics and photonics, and sensing and imaging probes for biomedical purposes. The conventional methods involve the use of diarylborinic acids or anhydrides and triaryl boranes, which are made from organometallic reagents. The strong nucleophilicity of these reagents limits the peripheral modifications onto the boron cores. Here, we report a metal-free one-pot synthesis of four-coordinate organoborons using boronic acids, which represents the first instance of ligand assisted organic group migration between boronic acids. A tetrahedral boron 'ate' complex capable of transferring an organic group to the adjacent sp2 boron within a boronic anhydride intermediate is proposed and preliminary mechanistic studies by MALDI-TOF and 11B NMR support this proposal. The products are available from a series of N,O-, N,N- and O,O-bidentate ligands upon a wide array of boronic acids. We anticipate that this reaction will impact the way of producing the four-coordinate organoborons, and propel a new discovery of such materials for optoelectronic and biomedical applications.
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