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A Comparative Study on the Thermodynamics of Halogen Bonding of Group?10 Pincer Fluoride Complexes.

ABSTRACT: The thermodynamics of halogen bonding of a series of isostructural Group?10 metal pincer fluoride complexes of the type [(3,5-R₂ -^tBu POCOP^tBu )MF] (3,5-R₂ -^tBu POCOP^tBu =?³ -C₆ HR₂ -2,6-(OPtBu₂ )₂ with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes?1-tBu (R=tBu, M=Ni), 2-H (R=H, M=Pd), 2-tBu (R=tBu, M=Pd), 2-COOMe (R=COOMe, M=Pd) and 3-tBu (R=tBu, M=Pt) form strong halogen bonds with Pd complexes showing significantly stronger binding to iodopentafluorobenzene. Structural and computational analysis of a model adduct of complex?2-tBu with 1,4-diiodotetrafluorobenzene as well as of structures of iodopentafluorobenzene in toluene solution shows that formation of a type?I contact occurs.

SUBMITTER: Joksch M

PROVIDER: S-EPMC7154528 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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A Comparative Study on the Thermodynamics of Halogen Bonding of Group 10 Pincer Fluoride Complexes.

Joksch Markus M Agarwala Hemlata H Ferro Monica M Michalik Dirk D Spannenberg Anke A Beweries Torsten T

Chemistry (Weinheim an der Bergstrasse, Germany) 20200228 16

The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5-R2 -tBu POCOPtBu )MF] (3,5-R2 -tBu POCOPtBu =κ3 -C6 HR2 -2,6-(OPtBu2 )2 with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1-tBu (R=tBu, M=Ni), 2-H (R=H, M=P ...[more]

PMID: 31846108

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Project description:Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-?(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(?-OAr(P)-1?(1)O,2?(1)P)3M(0), M = Ni (3-Ni), Pd (3-Pd), and Pt (3-Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3-Ni with two further U-Ni complexes XU(IV)(?-OAr(P)-1?(1)O,2?(1)P)3Ni(0), X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U-M bonds are significantly shorter than any other crystallographically characterized d-f-block bimetallic, even though the ligand flexes to allow a variable U-M separation. Excellent agreement is found between the experimental and computed structures for 3-Ni and 3-Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U-M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U-Ni bond than U-Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U-X adducts 3-Ni, 4, and 5. The data show a trend in uranium-metal bond strength that decreases from 3-Ni down to 3-Pt and suggest that exchanging the iodide for a fluoride strengthens the metal-metal bond. Despite short U-TM (transition metal) distances, four other computational approaches also suggest low U-TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3-Pd than 3-Ni, consistent with slightly larger U-TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal longer and weaker unsupported U-TM bonds vs 3.

Dataset Information

A Comparative Study on the Thermodynamics of Halogen Bonding of Group?10 Pincer Fluoride Complexes.

Publications

A Comparative Study on the Thermodynamics of Halogen Bonding of Group 10 Pincer Fluoride Complexes.

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