Eine neue Methode zur Darstellung prim�rer Phosphine

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [Cp*MCl4(PH2R)] (M = Nb, Ta; Cp* = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

“…Solvents were dried and freshly distilled under argon. The NMR spectra were recorded at 25°C (unless otherwise indicated) in CDCl 3 with an AVANCE DRX 400 spectrometer (Bruker), 1 [43], Ad [44], Cy [43], Ph [45], Mes [46]) were prepared according to literature procedures.…”

Organometallic Molybdenum(V) Complexes with Primary Phosphine Ligands. Syntheses, Spectroscopic Properties and Molecular Structures of [Cp°MoCl4(PH2R)] (R = But, 1‐Ad, Cy, Ph, 2, 4, 6‐Me3C6H2, 2, 4, 6‐Pri3C6H2, Cp° = C5EtMe4)

“…The melting points were determined in sealed capillaries under argon and are uncorrected. PH 2 R (R ϭ Bu t [26,27], 1-Ad [28], Cy [26], Ph [29], Mes [27,30], Tipp [31]) were prepared by literature procedures.…”

“…Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-221395 (1), Ϫ392 (2), Ϫ390 (3), Ϫ391 (4), Ϫ396 (6), Ϫ394 (7), and Ϫ393 (8 [26,27], Ad [28], Cy [26], Ph [29], Mes [27,30] Tipp [31]] is added to a suspension of [Cp°MoCl 4 ] in toluene, the solution turns red-brown with formation of the phosphine complexes [Cp°MoCl 4 (PH 2 R)] (Eq. 1).…”

Phosphine in the synthesis of organophosphorus compounds

“…The reactions of phosphine with alkyl chlorides (equimolar ratio, 280 8C, 5 days, activated carbon) afford mixtures of mono-, di-and trialkylphosphonium chlorides, monoalkylphosphonium chloride being the major product, which are converted into the corresponding phosphines on treatment with aqueous NaOH. 28 Having been bound in a complex on heating (70 ± 80 8C) with an equimolar amount of AlCl 3 , phosphine reacts with alkyl halides, 30 ± 31 cycloalkyl halides 30 and adamantyl bromide 32 to give, after the subsequent treatment of the reaction mixture with ice water and HCl, primary phosphines in 15% ± 83% yields. When alkyl iodides are used, phosphorylation is complicated by side processes.…”

“…Aryl halides do not enter into this reaction. 30 It should be noted that even when the complex PH 3 . AlCl 3 reacts with excess alkyl halide, the reaction occurs as monoalkylation; the formation of minor amounts of secondary phosphines was detected only for lower alkyl halides.…”