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Stable Actinide ? Complexes of a Neutral 1,4-Diborabenzene.

ABSTRACT: The ? coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related ? interactions of neutral heteroarenes including neutral bora-?-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, ? complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong ? donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, ?-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-?-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal ? donation and without significant ?/? backbonding contributions.

SUBMITTER: Paprocki V

PROVIDER: S-EPMC7496575 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene.

Paprocki Valerie V Hrobárik Peter P Harriman Katie L M KLM Luff Martin S MS Kupfer Thomas T Kaupp Martin M Murugesu Muralee M Braunschweig Holger H

Angewandte Chemie (International ed. in English) 20200525 31

The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting ...[more]

PMID: 32329111

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Project description:The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I(2)), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl-I(2) (1a), PCPPdBr-I(2) (2a), PCPPdI-I(2)(3a), PCPPdCl-F4DIBz (1b), PCPPdBr-F4DIBz (2b), and PCPPdBr-F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine being 24.6 (1a), 23.9 (2a), and 19.4% (3a) with X···I-I angles of 177, 176, and 179°, respectively. While the pincer palladium chloride 1 and bromide 2 were crystallographically isomorphous and showed similar XB behavior, the palladium iodide complex, 3, exhibited markedly different properties, and unlike 1 and 2 it does not, under similar conditions, result in XB complexes with the weaker XB donors F4DIBz and F8DIBu. The results indicate that PCPPdI is not nucleophilic enough to have XB interactions with other donors than iodine. However, the weaker XB donors F4DIBz and F8DIBu form XB complexes with the chloride 1 and especially with the bromide 2. The prevalence of the halogen bonding with 2 is probably not only electronic in origin, and it seems to offer the best balance between electron poorness and steric availability. The XB interactions with F4DIBz and F8DIBu are much weaker than with iodine, the reduction of the sum of the van der Waals radii of halogen to iodine being 13.5, 12.3, and 14.6% with C-I···X angles between 163 and 179° for 1b, 2b, and 2c, respectively, and results in polymeric (···1···F4DIBz···1···F4DIBz···)(n), (···2···F4DIBz···2···F4DIBz···)(n), and (···2···F8DIBu···2···F8DIBu···)(n) one-dimensional zigzag chains in the solid state.

Dataset Information

Stable Actinide ? Complexes of a Neutral 1,4-Diborabenzene.

Publications

Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene.

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