The open-chain triphosphanes RMe₂SiCH₂P(PR′₂)₂(R = Me, Ph; R′ = SiMe₃, Cy, Ph)

Abstract

The triphosphanes RMe(2)SiCH(2)P(PR'(2))(2) (R = Me, Ph; R' = SiMe(3), Cy) are synthesised in good yield via metathesis of organodichlorophosphanes and LiPR'(2), while for R' = Ph a propensity to form (Ph(2)P)(2) precludes isolation of the in situ characterised triphosphanes. Where R = Me and R' = SiMe(3) 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 (31)P{(1)H} 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.

Ruthenaphosphaalkenyls: Synthesis, Structures, and Their Conversion to η2-Phosphaalkene Complexes

“…In a manner similar to that previously described for 1 , the novel ruthena­phospha­alkenyls [Ru­{PCH­(SiMe 2 R)}­Cl­(CO)­(PPh 3 ) 2 ] (R = Me 2, Ph 3 , p- Tol 4 ) were obtained from the reaction of [RuHCl­(CO)­(PPh 3 ) 3 ] with excess of the respective phospha­alkyne RMe 2 SiCP , (Scheme ), the latter generated as toluene solutions by the double dehydrochlorination of RMe 2 SiCH 2 PCl 2 …”

“…General reagents were obtained from Sigma-Aldrich or Fisher and purified by appropriate methods before use; precious metal salts were obtained from STREM. [RuHCl­(CO)­(PPh 3 ) 3 ], t BuCP, RMe 2 SiCH 2 PCl 2 (R = Me, Ph), Me 3 SiCP, , and [Ru­{PCH­( t Bu)}­Cl­(CO)­(PPh 3 ) 2 ] , were prepared by literature methods. Unless otherwise stated, NMR spectra were recorded at 303 K on a Varian VNMRS 400 ( 1 H, 399.50 MHz; 13 C, 100.46 MHz; 19 F, 375.87; 31 P, 161.71 MHz; 29 Si, 79.37 MHz); VNMRS 500 ( 1 H, 499.91 MHz; 13 C, 125.72 MHz) or 600 ( 1 H, 599.69 MHz; 13 C, 150.81 MHz, 31 P, 242.83 MHz) spectrometers were used in selected instances.…”

Controlled Reactivity of Terminal Cyaphide Complexes: Isolation of the 5-Coordinate [Ru(dppe)2(C≡P)]+

“…Anhydrous ZnX 2 were further purified by extended heating at >200 °C under high vacuum (10 –7 mbar) and sublimation (>250 °C, 10 –7 mbar). Me 2 Mg, Me 3 SiCP, , [Ru­(dppe) 2 Cl]·OTf, and NaOPh were prepared by literature methods. Unless otherwise stated, NMR spectra were recorded at 303 K on a Varian VNMRS 400 ( 1 H, 399.50 MHz; 13 C, 100.46 MHz; 19 F, 375.87 MHz; 31 P, 161.71 MHz; 29 Si, 79.37 MHz) spectrometer.…”

Hydrochlorination of Ruthenaphosphaalkenyls: Unexpectedly Facile Access to Alkylchlorohydrophosphane Complexes

“…General reagents were obtained from Sigma-Aldrich or Fisher and purified by appropriate methods before use; precious metal salts were obtained from STREM. R­Me 2 Si­CH 2 Cl (R = p -C 6 H 4 CF 3 , n Bu), RMe 2 ­SiCH 2 ­PCl 2 (R = Me, Ph, Tol,), t BuCP, Me 3 ­SiCP, , [RuHCl­(CO)­(PPh 3 ) 3 ], and [Ru­{PCH­(R)}­Cl­(CO)­(PPh 3 ) 2 ] (R = t Bu, , SiMe 3 , SiMe 2 ­Ph, SiMe 2 ­Tol′) were prepared as previously described. Unless otherwise stated, NMR spectra were recorded at 303 K, on a Varian VNMRS 400 ( 1 H 399.50 MHz, 13 C 100.46 MHz, 19 F 375.87 MHz, 31 P 161.71 MHz, 29 Si 79.37 MHz).…”