137935-93-4Relevant academic research and scientific papers
NEW METHOD OF OBTAINING A STABLE DIPHOSPHIRANE
Bellan, Jacques,Etemad-Moghadam, Guita,Payard, Marc,Koenig, Max
, p. 1145 - 1146 (1986)
The stable monomer diphosphirane 2 is produced by the reaction of the diazomethane on the diphosphene 1.
Synthesis, structure, dynamics, and selective methylation of platinum and palladium diphosphametallacyclobutane complexes
Chapp, Timothy W.,Schoenfeld, Adam J.,Sanderson, Matthew D.,Chang, Cory L.,Glueck, David S.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.
, p. 5573 - 5585 (2013/01/14)
Treatment of M(dppe)Cl2 (M = Pd, Pt) or Pt((R,R)-Me-DuPhos) Cl2 with IsHPCH2PHIs (1; Is = isityl = 2,4,6-(i-Pr) 3C6H2) and 2 equiv of NaOSiMe3 gave the mononuclear diphosphametallacyclobutane complexes M(dppe)(IsPCH 2PIs) (M = Pd (2), Pt (3)), or Pt((R,R)-Me-DuPhos)(IsPCH 2PIs) (4). Dynamic processes involving phosphorus inversion and rotation about the P-C(Is) bonds in 2-4 were characterized by variable-temperature NMR spectroscopy, which suggested that each existed as a single C2-symmetric diastereomer in solution, consistent with their solid-state structures determined by X-ray crystallography. The MiniPhos derivative IsMePCH2PMeIs (5) was prepared as a 5.5/1 rac/meso mixture by sequential arylation and methylation of Cl2PCH 2PCl2. Alternatively, the catalyst precursor Pt((R,R)-Me-DuPhos)(Ph)(Cl) mediated alkylation of secondary phosphines in the presence of NaOSiMe3 to yield selectively meso-5 either from PHMe(Is) and CH2I2 or from 1 and MeI. Recrystallization and chromatography yielded diastereomerically enriched rac-5 and meso-5. Treatment of M(dppe)(OTf)2 (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)(OTf)2 with meso-5 gave the dications meso-[M(diphos)(IsMePCH2PMeIs)][OTf] 2 (M(diphos) = Pd(dppe) (6), Pt(dppe) (8), Pt((R,R)-Me-DuPhos) (10)). Similar reactions of rac-5 yielded the dications rac-[M(diphos)(IsMePCH 2PMeIs)][OTf]2 (M(diphos) = Pd(dppe) (7), Pt(dppe) (9)) and a 1/1 mixture of the C2-symmetric diastereomers [Pt((R,R)-Me-DuPhos)(IsMePCH2PMeIs)][OTf]2 (11a,b). Treatment of 2 and 3 with 2 equiv of methyl triflate gave the dications 6-9 as ca. 1/1 meso/rac mixtures, and methylation of 4 selectively gave one of the C2-symmetric diastereomers, 11a. These alkylations proceeded via the observable monomethylated intermediates [M(diphos)(IsMePCH2PIs)][OTf] (12-14).
Reductive Dehalogenation of (Cl,Br)RP-CH2-PR(Cl,Br) with Fe2(CO)9 - Formation of Complexes with Strained Diphosphirane Skeletons and Bifunctional Phosphido Bridges (μ2-PR)2CH2
Bitterer, F.,Brauer, D. J.,Doerrenbach, F.,Gol, F.,Knueppel, P. C.,et al.
, p. 1131 - 1144 (2007/10/02)
P-Halogen Functional Methylenebisphosphines, Oxidative Addition, Reductive Dehalogenation, Phosphido Complexes, Diastereoselective Complexation Reductive dehalogenation of the bifunctional methylene bridged halogenphosphines XRP-CH2-PRX (X = Cl, Br; R = i
