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• W2025555701 abstract "The complex [PtMe2(iPrBABAR-Phos)2] (3) was prepared in a clean and quantitative ligand substitution reaction from [PtMe2(cod)] (1; cod = η4-1,5-cyclooctadiene) and the phosphirane iPrBABAR-Phos (2). The structure of 3 was determined by X-ray diffraction. The Pt−P bonds (∼2.26 Å) lie in the shorter range of PtII−P bonds, although the 1J(195Pt31P) 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 Pt(0) 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." @default.
• W2025555701 created "2016-06-24" @default.
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• W2025555701 date "2003-04-30" @default.
• W2025555701 modified "2023-10-13" @default.
• W2025555701 title "Binding of Specialty Phosphines to Metals: Synthesis, Structure, and Solution Calorimetry of the Phosphirane Complex [PtMe₂(ⁱ^PrBABAR-Phos)₂]" @default.
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• W2025555701 doi "https://doi.org/10.1021/om020642q" @default.
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