Synthesis of new acyclic aminophosphites and their chelate complexes with rhodium(i) and palladium(ii)

Abstract

New acyclic aminophosphites (RO)2POCH2CH2NMe2 (PN) (R = Et. Pr'. or adamantyl) characterized by various steric requirements of the phosphorus center were synthesized. The reacnons of [he aminophosphites with Pd(COD)CI 2 (COD is 1.5-cyclooctadiene) and [Rh(CO)~C1]_~ afforded the stable chelate mononuclear complexes PdCI2(PN) and RhCICO(PN}. respectively. The structures of the resulting compounds were established by ~H, ~3C. and 31p NMR and IR spectroscopy, X-ray diffraction analysis, laser and plasma desorption mass spectrometry, X-ray photoelectron spectroscopy, and sedimentation analysis.

Iminophosphites as new chiral P,N-bidentate ligands

“…An increase in the electron-donor ability of a nitrogen-containing unit causes a decrease of 1 J(P,Rh) (Table 1). A similar behaviour was observed when the spectral parameters of 2a and its recently obtained 11 analogue 5 [R = Pr i , n(CO) 2022 cm -1 (CHCl 3 ), 1 J(P,Rh) 261.7 Hz (CDCl 3 )] were compared. † † Crystallographic data for 2a: at -80 °C crystals of C 18 H 28 ClNO 4 PRh are monoclinic, space group P2 1 , a = 9.042(4), b = 8.727(4), c = = 13.904 (7) Å, b = 92.32(4)°, V = 1096.3(9) Å 3 , Z = 2, M = 491.74, m(MoKα) = 0.995 mm -1 , 2778 reflections were measured, 2567 (R int = = 0.0443) independent reflections were used in all calculations.…”

“…14 The presence of a Pd-P bond in the complexes 3a,b is proved by d P and ∆d P values (Table 2) typical of six-membered palladium chelates with acyclic nitrogen-containing phosphites. 15 Two equally intense n(Pd-Cl) bands in the far IR region of 3a,b result from the cis-configuration of chlorine ligands and different trans-influences of phosphorus and nitrogen centres (Table 2).…”

The First Example of Coordination of a Tricyclic Hydrophosphorane to Platinum(II). X-ray Crystal Structure of an Unusual Platinated Phosphorane

“…Mass spectra were recorded on a MSVKh TOF spectrometer with ionization by californium-252 fission fragments (plasma desorption technique). Sedimentation analyses were performed on a MOM-3180 analytical ultracentrifuge following the known procedures . Elemental analyses were performed at the Laboratory of Microanalysis (A. N. Nesmeyanov Institute of Organoelement Compounds, Moscow).…”