Elektrophile Aktivierung von OH-Gruppen in Phosphor-organischen Verbindungen - Eine Anwendung für Phosphan-Borane / Electrophilic Activation of OH Groups in Organophosphorus Compounds - An Application of Phosphane Boranes

Abstract

In the synthesis of oligophosphane ligands containing the neopentyl framework, the electrophilic activation of an OH group in com pounds of the type R′CH2C(CH2OH)(CH2PR2)2 is a serious problem which may be overcome by BH3 protection of the intrinsically nucleophilic phosphane groups. It is shown that the hydroxy group of HOCH2C(CH2PPh2)3 (1) may be mesylated to yield MsOCH2C(CH2PPh2BH3)3 (3) after protection of 1 as its BH3 derivative (2).

Tripodal Phosphane Ligands with Novel Linker Units and Their Rhodium Complexes as Building Blocks for Dendrimer Catalysts

“…These were characterised by the analytical and NMR spectroscopic techniques applied to the phosphane precursors as well as (1) 2.180(6), P(2)ϪC(48) 1.843(6), O(2)ϪC(51) 1.55(2), RhϪC(2) 2.155(6), P(3)ϪC(47) 1.849(6); P(1)ϪRhϪP (2) 87.56(6), P (1)ϪC (46)ϪC (45) 115.0(4), C(49)ϪO (1)ϪC (50) 112.9(5), P(1)ϪRhϪP(3) 87.11(5), P(2)ϪC (48) (50)ϪC (51) 109.5(6), P(2)ϪRhϪP (3) 89.52(5), P(3)ϪC (47)ϪC (45) 117.4(4), C(50)ϪC(51)ϪO(2) 100.8(9); b) ligand arrangement in the first coordination sphere of complex 11b; c) the packing of the molecules of 11b in the unit cell; for the sake of clarity, the phenyl groups of the diphenylphosphane units, and the lattice solvent molecules (CH 2 Cl 2 ) have been omitted (14) by electrospray mass spectrometry, which confirmed the uniformity of the products. The molecular ion peaks were observed at m/z ϭ 1002.…”

Tridentate phosphine ligands with novel linker-units

“…The reaction mixture was stirred at room temperature for 7 d. All volatiles were removed subsequently, the residue was taken up in 10 ml of toluene, washed with 3 × 10 ml degassed water and the organic phase was dried over Na 2 SO 4 . The solvent was removed in vacuo and the crude product reprecipitated at Ϫ30 ЊC from methanol giving HC᎐ ᎐ ᎐ C-CH 2 OCH 2 C(CH 2 PPh 2 ) 3 (11) as a soft colourless solid.…”

“…: C 75.18, H 6.58; found: C 74.87, H 6.41%. Preparation of HC᎐ ᎐ ᎐ C-CH 2 OCH 2 C(CH 2 PPh 2 ) 3(11)…”