The triphosphanes RMe2SiCH2P(PR′2)2 (R = Me, Ph; R′ = SiMe3, Cy) are synthesised in good yield viametathesis of organodichlorophosphanes and LiPR′2, while for R′ = Ph a propensity to form (Ph2P)2 precludes isolation of the in situ characterised triphosphanes. Where R = Me and R′ = SiMe3 the triphosphane has also been characterised by single crystal X-ray diffraction and exhibits a single geometric conformer in the solid state, though solution-phase NMR spectra are indicative of facile conformational exchange across a wide temperature range. All of the described triphosphanes exhibit comparable behaviour, with their respective 31P{1H} NMR spectra manifesting anomalous ‘second-order’ characteristics, which are considered using full spin-Hamiltonian simulation. Preliminary studies of coordination chemistry and ancillary reactivity of the triphosphanes are described.
