Dataset Information

Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

ABSTRACT: Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C₆H₄)₂, tethered by a phenylene linker to a -PⁱPr₂ anchor, with group 10 complexes L₂M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)Pt^II(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ²-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.

SUBMITTER: Hwang SJ

PROVIDER: S-EPMC7806272 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

Hwang Seung Jun SJ Tanushi Akira A Radosevich Alexander T AT

Journal of the American Chemical Society 20201211 51

Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable ...[more]

PMID: 33306370

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Project description:Heterobimetallic complexes containing short uranium-group 10 metal bonds have been prepared from monometallic IU(IV)(OAr(P)-κ(2)O,P)3 (2) {[Ar(P)O](-) = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U-M bond in IU(IV)(μ-OAr(P)-1κ(1)O,2κ(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)(μ-OAr(P)-1κ(1)O,2κ(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

Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

Publications

Enthalpy-Controlled Insertion of a "Nonspectator" Tricoordinate Phosphorus Ligand into Group 10 Transition Metal-Carbon Bonds.

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