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Expanding the allyl analogy: accessing ?3-P,B,P diphosphinoborane complexes of group 10.

ABSTRACT: Using the diphosphinoborane, (PPh2)2BMes (Mes = 2,4,6-Me3C6H3), we report the first examples of ?3-P,B,P-ligated complexes using Ni(0) and Pt(ii). Reaction of (PPh2)2BMes with Ni(COD)2 or Pt(COD)Me2 (COD = 1,5-cyclooctadiene) results in gradual COD displacement to give [?3-P,B,P-(PPh2)2BMes]Ni(COD) (3) or [?3-P,B,P-(PPh2)2BMes]Pt(CH3)2 (6). Complex 3 serves as a versatile Ni-containing synthon for the preparation of square planar or tetrahedral Ni(0) complexes. Notably, the M-B interaction in these systems is non-negligible - with coordination resulting in an upfield shift of ca. 80 ppm in the 11B NMR spectrum. We also show that treatment of the PtIV halide precursor, [PtMe3I]4 with this ligand framework results in migration of X-type ligands (CH3- and I-) to boron and reductive elimination of ethane (C2H6) to give a distorted square planar zwitterionic PtII complex, Pt[?2-P,P-(PPh2)2B(Mes)(CH3)][?2-P,P-(PPh2)2B(Mes)(I)] (10). This reactivity suggests the feasibility of (PPh2)2BMes-ligand-induced labilization of M-X ligands.

SUBMITTER: Drover MW

PROVIDER: S-EPMC6005356 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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Expanding the allyl analogy: accessing η3-P,B,P diphosphinoborane complexes of group 10.

Drover Marcus W MW Peters Jonas C JC

Dalton transactions (Cambridge, England : 2003) 20180301 11

Using the diphosphinoborane, (PPh2)2BMes (Mes = 2,4,6-Me3C6H3), we report the first examples of η3-P,B,P-ligated complexes using Ni(0) and Pt(ii). Reaction of (PPh2)2BMes with Ni(COD)2 or Pt(COD)Me2 (COD = 1,5-cyclooctadiene) results in gradual COD displacement to give [η3-P,B,P-(PPh2)2BMes]Ni(COD) (3) or [η3-P,B,P-(PPh2)2 ...[more]

PMID: 29441396

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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

Expanding the allyl analogy: accessing ?3-P,B,P diphosphinoborane complexes of group 10.

Publications

Expanding the allyl analogy: accessing η<sup>3</sup>-P,B,P diphosphinoborane complexes of group 10.

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