Bildung und Eigenschaften von Acylphosphanen. VI. Synthese von Alkyl‐ und Arylbis (trimethylsilyl)‐ sowie Alkyl und Aryltrimethylsilyphosphanen

Abstract

Methoden zur Synthese von Alkyl‐und Arylbis (Trimethylsilyl)‐sowie Alkyl‐und Aryltrimethylsilylphosphanen werden beschrieben. Die zur Darstellung der Titelverbindungen benötigten primären Phosphane wurden nach bekannten Methoden (Reduktion mit LiAlH4) synthetisiert. Alkyl‐ und Arylbis(trimethylsilyl)phosphane sind aus den entsprechenden Dilithiumphosphiden (Primäres Phosphan und Methyllithium) und Trimethylchlorsilan oder aus Lithiumbis (trimethylsily) phosphid und Alkylhalogeniden zugänglich. Geeignete Synthesen für Alkyl‐und Aryltrimethylsilyphosphane sind die Umsetzungen der Alkyl‐und Aryllithiumphosphide mit Trimethylchlorsilan (Ausnahme; Methyl) sowie der Alkyl‐ und Arylbis (Trimethylsilyl) phosphane mit Methanol. Die Reaktion zwischen Phenylbis (trimethylsilyl)‐Phosphan und wasser wurde naher untersucht und die Bildung von Trimethylsilanol 1H‐NMR‐ spektroskopisch nachgewiesen. Lithiumtrimethylsilylphosphide reagieren mit 2, 2‐Dimethylpropionylchlorid zu den (2,2‐Dimethylplropionyl) trimethylsilyphosphanen (Ketoformen).

Erratum: Synthesis of functional phosphines with ortho‐substituted aryl groups: 2‐RC6H4PH2 and 2‐RC6H4P(SiMe3)2 (R = i‐Pr‐ or t‐Bu)

“…The products were analyzed by 31 P NMR spectroscopy (3: δ = 164, 4: δ = 166). These chemical shifts are similar to related dichloroarylphosphines such as MesPCl 2 (δ = 167) [32]. Reduction of the dichlorides 3 and 4 using LiAlH 4 affords primary phosphines 5 and 6 in good isolated yield (70% and 82%, respectively).…”

“…Although phosphine 5 has previously been mentioned, its synthesis and characterization were not reported [33]. Analysis of the products using 31 [32]. Compounds 5 and 6 were further characterized by 1 H and 13 C{ 1 H} NMR spectroscopy, and mass spectrometry, each of which supported the assigned structures.…”

Inversely Polarized Phosphaalkenes as Phosphinidene‐ and Carbene‐Transfer Reagents

“…The phosphaalkenes tBuP=C(NMe 2 ) 2 (1a), [20] CyP=C(NMe 2 ) 2 (1b), [21] PhP=C(NMe 2 ) 2 (1d), [22] MesP=C(NMe 2 ) 2 (1e), [20] and Me 3 SiP=C(NMe 2 ) 2 (1i), [23] as well as Ph 2 C=C=O, [24] AdPH 2 , [25] tBuP(H)SiMe 3 , [26] thiouronium salt 7, [27] and (tBuP) 3 [28] were prepared as described in the literature. Infrared spectra were recorded with a Bruker FT-IR IFS 66 spectrometer.…”

Synthesis, structure and π-delocalization of a phosphaalkenyl based neutral PNP-pincer

“…Solvents were dried with a PureSolve system and degassed prior to use. Mes-PTMS 2 [21] and 2,6-bis(chlorocarbonyl)pyridine [22] were prepared according to published procedures. All other chemicals were obtained from Sigma–Aldrich or ABCR and used as received.…”