Electrophilic ring-opening of [(RP)nAs]− anions; a simple route to functionalised neutral phosphines of the type [(ButP)(ButRP)2]

Access to catenated and branched polyphosphorus ligands and coordination complexes via a tri(pyrazolyl)phosphane

“…18b Wright and co-workers were the first to prove that a triphosphane can indeed be coordinated intact to a transition metal. 10 The isolation of complex 10 shows that this is also valid for iso-tetraphosphanes. The complexes 9 and 10 are characterized by distinct carbonyl stretching vibrations (9: 2044, 1972, 1930, 1916(sh); 10: 2039, 1969, 1920(sh) cm À1 ), which are reminiscent of the two a 1 and one e stretching vibrations of C 3v symmetric [Fe(CO)] 4 19 moieties but indicative of the overall lower symmetry of the compounds.…”

P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

“…[21] This notion is supported by reactions of 5b[OTf] with one equivalent CuOTf·4 CH 3 CN and AgOTf, which yield the expected coordination complexes 10[OTf] 2 and 11[OTf] 2 , respectively.T he molecular structures of these compounds contain the intact triphosphane 5b + . [32] The 31 PNMR spectra of the isolated complexes give rise to ab roadened AX 2 spin system (10 2+ : d(P A ) = À56.4, d(P X ) = À16.5, 1 J(P A P X ) = À195 Hz and 11 2+ : d(P A ) = À57.7, d(P X ) = À7.2, 1 J(P A P X ) = À191 Hz), being only slightly shifted compared to the free ligand (see above). [21] Single crystals suitable for X-ray analysis were obtained by slow diffusion of Et 2 Oi nto as aturated CH 3 CN solution of 10[OTf] 2 (Figure 4).…”

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

“…Though single crystals of 8 and 9 have thus far proven elusive, their identity is clear from spectroscopic data. Both retain the characteristic AM 2 coupling patterns in their 31 P{ 1 H}-NMR spectra, though with 13 C, 29 Si, 195 Pt) are internally consistent. It is, however, noteworthy that an unusually large 3 J PH coupling (~20 Hz), noted in the free ligands between the central phosphorus atom and cyclohexyl CH units, has been lost upon coordination, presumably as a consequence of conformational change.…”

“…Notwithstanding, open-chain triphosphanes remain the least well studied of such materials, though recent notable reports have included isolation of the stable 1,3-dihydrotriphosphane (TbtHP) 2 PFc (Fc = ferrocenyl, Tbt = 2,4,6-{CH(SiMe 3 ) 2 } 3 -C 6 H 2 ), 10 extrusion of DmpP(PPh 2 ) 2 (Dmp = 2,6-Mes 2 C 6 H 3 ) from the terminal zirconium phosphinidene [Cp 2 Zr PDmp(PMe 3 )] with Ph 2 PCl, 11 formation of HP{P(H)( t Bu)→W(CO) 5 } 2 via a Cp* ring-expansion protocol 12 and the electrophilic ring-opening of ( t BuP) 3 As to afford t BuP(P t BuR) 2 (R = Me, benzyl, allyl). 13 Typically, however, the triphosphanes are ancillary to the prevailing foci, thus relatively few examples have been comprehensively characterised. This is particularly so with respect to more reactive species bearing hydride or silyl substituents at phosphorus, the range of which is limited to (TbtHP) 2 PFc, 10 Me 3 SiP{PR 2 } 2 (R = N i Pr 2 , 14 Ph, 14 t Bu 15 ) and P{PMe(SiMe 3 )} 3 .…”