Coordination of Phosphinoboranes R2PB(C6F5)(2) to Platinum: An Alkene-Type Behavior

Université de Toulouse , UPS, LHFA, 118 Route de Narbonne, F-31062 Toulouse, France.
Journal of the American Chemical Society (Impact Factor: 12.11). 04/2012; 134(15):6560-3. DOI: 10.1021/ja301929n
Source: PubMed

ABSTRACT The paucity of boron-containing heteroalkene complexes prompted us to explore the coordination of phosphinoboranes. The complexes {[R(2)PB(C(6)F(5))(2)]Pt(PPh(3))(2)} (R = Cy, t-Bu) were obtained by ethylene displacement. Spectroscopic and crystallographic data indicated symmetric side-on coordination of the phosphinoborane to Pt. Thorough analysis of the bonding situation by computational means revealed important similarities but also significant differences between the phosphinoborane and ethylene complexes.

15 Reads
  • [Show abstract] [Hide abstract]
    ABSTRACT: Over the last few years, the coordination of phosphine-boranes and related Frustrated Lewis Pairs to transition metals has attracted considerable interest. These polyfunctional, ambiphilic ligands are very versatile. In particular, the Lewis acid site may participate in different ways to coordination, directly at the metal or in near periphery. These recent achievements are presented and discussed in this chapter.
    Topics in current chemistry 09/2012; 334. DOI:10.1007/128_2012_370 · 4.46 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Cationic half-sandwich ruthenium complexes featuring kappa(2)-bound aminoborane ligands can readily be accessed from 16-electron precursors via chloride abstraction in the presence of H2BNR2 (R = Pr-i, Cy). Complexes [Cp*Ru(L) (kappa(2)-H2BNR2)][BAr4f] (2a: R = Pr-i, L = PCy3; 2b: R = Pr-i, L = PPh3; 2c: R = Pr-i, L = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; 3a: R = Cy, L = PCy3; Ar-f = C6H3(CF3)(2)-3,5) were isolated in yields of similar to 60%, and characterised in the solid state by X-ray crystallography (for 2a, 2c, and 3a). Low-field B-11 NMR shifts for the coordinated aminoborane fragment, together with short Ru center dot center dot center dot B contacts (of the order of 1.97 angstrom) imply a relatively tightly bound borane ligand, a finding which is given further credence by the results of density functional theory studies (e.g. bond dissociation energies in the range 24 kcal mol(-1); 1 kcal mol(-1) = 4.186 kJ mol(-1)). In terms of reactivity, kappa(2) systems of this type, while potentially offering a versatile route to asymmetric kappa(1) systems, in fact undergo borane extrusion even in the presence of a single equivalent of added ligand.
    Australian Journal of Chemistry 01/2013; 66(10). DOI:10.1071/CH13106 · 1.56 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The PB chain gang: The reactions of an acetylene complex of titanocene with the parent phosphinoborane stabilized only by a Lewis base lead to novel phosphinoborane oligomers coordinated by {Cp2 Ti} complex fragments. Depending on the reaction conditions (temperature and stoichiometry), unprecedented oligomeric chains of phosphinoborane are obtained by dehydro-oligomerization and PP coupling reactions.
    Angewandte Chemie International Edition 05/2013; 52(19). DOI:10.1002/anie.201209703 · 11.26 Impact Factor
Show more