L. Riesel

N-PHOSPHANYLATED 1.3.2-OXAZA- AND 1.3.2-DIAZAPHOSPHOLANES AND -PHOSPHORINANES

Abstract The formation of the N-phosphanyl derivatives of the oxaza- and diazaphosphorinanes and -phospholanes 2-10 by the reaction of PX3 (X = Cl, Br) with alcoholamines and diamines is described. The unusually large 2 J PNP coupling constants of the products are discussed.

1-Methyl-2-Chlor-3-Dichlorphosphinyl- und 1-Methyl-2-Methoxy-3-Dimethoxyphosphinyl-1,3,2λ3-Diazaphosphorinan Als Liganden in ÜBergangsmetallkomplexen; Synthese und Struktur von Tetracarbonyl-MolybdäN(0)-Koordinationsverbindungen und Eines Ionischen Bis-Chelat-Platin(II)-Chlorid-Komplexes

Abstract The reaction of 1-methyl-2-chloro-3-dichlorophosphinyl-1,3,2λ3-diazaphosphorinane 1 with (norbornadiene)tetracarbonylmolybdenum(0) in a 2:1 molar ratio furnished cis-bis(1-methyl-2-chloro-3-dichlo-rophosphinyl-1,3,2-diazaphosphorinane)tetracarbonylmolybdenum(0) 2. In 2, one ligand 1 is bonded to Mo(0) via the Pcl group, the other through the Pl2 group. 1-Methyl-2-methoxy-3-dimethoxyphos-phinyl-1,3,2λ3-diazaphosphorinane 3 reacted with norbornadienetetracarbonyl-molybdenum(0) to form the chelate complex cis-(1-methyl-2-methoxy-3-dimethoxyphosphinyl-1,3,2-diazaphosphorinane)tetracarbonylmolybdenum(0) 4, in which one molecule of the ligand 3 is attached to Mo(0) in a chelating fashion, coordinating through both the POCH3 and the P(OCH3)2 group. In the reaction of 3 with (COD)PtCl2 (COD = 1,5-cyclooctadiene) in a 2:1 molar ratio the ionic bis-chelate complex cis-bis(1-methyl-2-methoxy-3-dimethoxyphosphinyl-1,3,2-diazaphosphorinane)-platinum(II)chloride 5 was formed. Two molecules of 3 are coordinated...

ON DERIVATISATION REACTIONS OF 2-CHLORO-3-DICHLOROPHOSPHANYL-1.3.2- OXAZAPHOSPHORINANE

Abstract Derivatisation reactions of 2-chloro-3-dichlorophosphanyl-1.3.2-oxazaphosphorinane lb with protic nucleophiles like HNEt2, C2H5OH, CH2OH and the Franz-reagent NEt33HF forming the substituted N-phosphanylphosphorinanes 2-10 are described. Furthermore the temperature dependence of the 2 J PNP-coupling constant of 2-chloro-3-dichlorophosphanyl-1.3.2-oxazaphosphorinane lb and 2-diethylamino-3-bis(diethylamino)phosphanyl-1.3.2-oxazaphosphorinane 2 in a range from 203 K to 353 K was investigated.

ON DERIVATISATION REACTIONS OF 2-CHLORO-3-DICHLOROPHOSPHANYL-1-METHYL-1.3.2-DIAZAPHOSPHORINANE

Abstract Derivatisation reactions of 2-chloro-3-dichlorophosphanyl-1-methyl-1.3.2-diazaphosphorinane 1 with protic nucleophiles like HNEt2, CH3OH, C2H5OH and the Franz-reagent NEt33HF forming the substituted N-phosphanyldiazaphosphorinanes 2-12 are described. The preferential nucleophilic attack on the exocyclic phosphanyl group of 1 in partial replacement reactions is discussed by means of 31P-, 1H- and 13C-NMR data.