109152-83-2Relevant academic research and scientific papers
Germanium(II) and tin(II) complexes of a sterically demanding phosphanide ligand
Izod, Keith,Stewart, John,Clark, Ewan R.,Clegg, William,Harrington, Ross W.
experimental part, p. 4698 - 4707 (2010/08/13)
The reaction between PhPCl2 and 1 equiv of RLi, followed by in situ reduction with LiAlH4 and an aqueous workup yields the secondary phosphane PhRPH [R = (Me3Si)2CH]. Treatment of PhRPH with n-BuLi in diethyl ether generates the lithium phosphanide (RPhP)Li(Et 2O)n [15(Et2O)], which may be crystallized as the tetrahydrofuran (THF) adduct (RPhP)Li(THF)3 [15(THF)]. Compound 15(Et2O) reacts with 1 equiv of either NaO-tBu or KO-tBu to give the corresponding sodium and potassium phosphanides (RPhP)Na(Et2O) n (16) and (RPhP)K(Et2O)n (17), which may be crystallized as the amine adducts [(RPhP)Na(tmeda)]2 [16(tmeda)] and [(RPhP)K(pmdeta)]2 [17(pmdeta)], respectively. The reaction between 2 equiv of 17 and GeCl2(1,4-dioxane) gives the dimeric compound [(RPhP)2Ge]2'Et2O (18'Et2O). In contrast, the reaction between 2 equiv of 15 and SnCl2 preferentially gives the ate complex (RPhP)3SnLi(THF) (19) in low yield; 19 is obtained in quantitative yield from the reaction between SnCl2 and 3 equiv of 15. Crystallization of 19 from n-hexane/THF yields the separated ion pair complex [(RPhP)3Sn][Li(THF)4] (19a); exposure of 19a to vacuum for short periods leads to complete conversion to 19. Treatment of GeCl2(1,4-dioxane) with 3 equiv of 15 yields the contact ion pair (RPhP)3GeLi(THF) (20), after crystallization from n-hexane/THF. Compounds 15(THF), 16(tmeda), 17(pmdeta), 18'Et2O, 19a, and 20 have been characterized by elemental analyses, multielement NMR spectroscopy, and X-ray crystallography. While 15(THF) is monomeric, both 16(tmeda) and 17(pmdeta) are dimeric in the solid state. The diphosphagermylene 18'Et2O adopts a dimeric structure in the solid state with a syn,syn-arrangement of the phosphanide ligands, and this structure appears to be preserved in solution. The ate complex 19a crystallizes as a separated ion pair, whereas the analogous ate complex 20 crystallizes as a discrete molecular species. The structures of 19 and 20 are retained in non-donor solvents, while dissolution in THF yields the separated ion pairs 19a and [(RPhP)3Ge][Li(THF)4] (20a).
Linear Oligophosphaalkanes, XIX. - Partial Alkylation of Phenylphosphane with Dihalomethanes CH2X2 (X = Cl, Br) - A Facile Synthesis of Methylenebis(phenylphosphane), HPhP-CH2-PPhH
Langhans, Klaus P.,Stelzer, Othmar
, p. 1707 - 1712 (2007/10/02)
The reaction of PhPHNa with CH2X2 (X = Cl, Br) in tetrahydrofuran affords methylenebis(phenylphosphane), HPhP-CH2-PPhH (2), phenylphosphane, methylphenylphosphane, PhPHMe, and 1,2,3,4-tetraphenylcyclo-5-carba-1,2,3,4-tetraphosphane, CH2(PPh)4 (3).HPhP-CH2-PPhH (2) may be obtained in a facile one-step synthesis with yields up to 70percent by reaction of PhPH2 with CH2Cl2 and KOH in dimethyl sulfoxide/H2O or dimethylformamide/H2O.The formation of PhPHMe and CH2-(PPh4)4 may be explained by a reaction scheme including P-phenylphosphaalkene PhP=CH2 and HPhP-CH2Cl as reactive intermediates.The reactions between PhPHM (M = Na, K) and CH2Cl2 or CH2Br2 respectively, have been studied by independent experiments.
