Binding of specialty phosphines to metals: Synthesis, structure, and solution calorimetry of the phosphirane complex [PtMe2((iPr)BABAR-Phos)(2)]

C Laporte, G Frison, H Grutzmacher, A C Hillier, W Sommer, Steven Patrick Nolan

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22 Citations (Scopus)

Abstract

The complex [PtMe2((iPr)BABAR-Phos)(2)] (3) was prepared in a clean and quantitative ligand substitution reaction from [PtMe2(cod)] (1; cod = eta(4)-1,5-cyclooctadiene) and the phosphirane (iPr)BABAR-Phos (2). The structure of 3 was determined by X-ray diffraction. The Pt-P bonds (similar to2.26 Angstrom) lie in the shorter range of Pt-II-P bonds, although the (1)J((PtP)-Pt-195-P-31) coupling (1840 Hz) is quite small. The enthalpy for this ligand substitution reaction was measured by solution calorimetry and found to be exothermic by 11.8 kcal/mol, a relatively low exothermicity for a reaction involving a tertiary phosphine in this Pt system. Calculations using density functional theory (DFT) on the B3LYP level were applied using the simplified model reaction [PtH2(cod)] + 2(H2N)PC2H4 --> [PtH2{(H2N)PC2H4}(2))] + cod, and these also gave a rather low substitution enthalpy (-17 kcal/mol). A charge decomposition analysis (CDA) was performed for Pt(II) and NO complexes with the simple P-amino phosphirane (H2N)PC2H4 and PH3 as ligands. Contrary to expectations, it is found that the phosphirane acts as a relatively good electron donor, while its electron-acceptor properties are not significantly different from those of other phosphines. The particularly low reaction enthalpy may thus be due to a low directionality of the donor orbitals toward the metal center.

Original languageEnglish
Pages (from-to)2202-2208
Number of pages7
JournalOrganometallics
Volume22
Issue number11
DOIs
Publication statusPublished - 26 May 2003

Keywords

  • LIGANDS
  • PHOSPHORUS
  • FRAGMENT
  • CRYSTAL
  • RING
  • THERMOCHEMISTRY
  • PLATINUM(II)
  • INSERTION
  • ORBITALS
  • ENERGIES

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