Secondary Arsines Research Articles

Divergent Reactivity of Phosphapalladacycles toward E–H (E = N, P, As) Bonds

Secondary arsines were observed to decomplex strongly chelating phosphapalladacycles rapidly under mild conditions. As–H bond migration led to ortho-protonation of the C,P ligand. On the other hand, N–H and P–H bonds in amine and phosphine analogues were acidified under the same conditions and no ligand decomplexation of the metallacycle was observed. Subsequently, secondary arsines bearing the As–H bond were applied in deuteration by directed ortho-metalation (DoM) and decomplexation strategies. In the former, HAsPh2 was a convenient deuterium shuttle which facilitated the ortho-deuteration of DoM-palladacycle intermediates under neutral conditions. High deuterium incorporation (>99%) was achieved without specialized preformed deuterating agents. In the latter, HAsPh2 afforded the preligands of monomeric, dimeric, bidentate, and tridentate complexes of Pd in excellent yields of 95–98% within 30 min at room temperature. Key reaction steps for the intramolecular insertion of As–H into the Pd–C bond were ou...

ChemInform Abstract: Primary and Secondary Neopentyl Arsines and Their Reactions with Trimethylgallium. Crystal and Molecular Structure of (Me2GaAs(CH2CMe3) 2)2.

Abstract The primary and secondary neopentylarsines, NpAsH 2 and Np 2 AsH (Np  CH 2 CMe 3 ) have been prepared from the reaction of the corresponding bromide (NpAsBr 2 and Np 2 AsBr) with lithium aluminum hydride in ether or tetraglyme solution. Reaction of the primary or secondary arsine with GaMe 3 yielded a colorless, crystalline arsino(gallane) with empirical formula Me 2 GaAs(H)Np or Me 2 GaAsNp 2 , respectively. The new compounds have been fully characterized according to elemental analysis, physical and solubility properties, IR, 1 H and 13 C NMR spectroscopies. Single crystal X-ray diffraction studies of Me 2 GaAsNp 2 have shown the compound to be dimeric in the solid stare. The compound [Me 2 GaAsNp 2 ] 2 crystallized in the triclinic space group P 1 with unit cell parameters a =8.688(4), b =9.817(4), c =9.910(4) A, V =774.7(6) A 3 and Z =2. The planar (GaAs) 2 ring of the dimer lies on an inversion center with GaAs bond lengths of 2.529(1) and 2.532(1) A. The endocyclic angles at As and Ga are 94.3(1) and 85.7(1)°, respectively.

ChemInform Abstract: Reaction of Secondary Arsine Oxides with Acids.

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Tetraalkyldiarsines As Potential Precursors for Electronic Materials: Synthesis and Characterization Of Various Iso-Propyl Arsenic Compounds

AbstractTetrakis(iso-propyl)diarsine was synthesized by the reaction of (i-Pr)2AsLi with (i-Pr)2AsI. The lithium salt of the secondary arsine was produced following deprotonation of (i-Pr)2AsH, obtained by reduction of (i-Pr)2AsI, which was prepared by the thermolysis of (i-Pr)3Asl2. The X-ray crystal structure of \(i-Pr)3AsI]\I] has been determined on the product of the reaction of (i-Pr)3As and 12. Compounds of the general form E=As(i-Pr)3 (E = O, S, Se) have been prepared.

Primary and secondary neopentyl arsines and their reactions with trimethylgallium. Crystal and molecular structure of [Me 2GaAs(CH 2CMe 3) 2] 2

The primary and secondary neopentylarsines, NpAsH 2 and Np 2AsH (Np  CH 2CMe 3) have been prepared from the reaction of the corresponding bromide (NpAsBr 2 and Np 2AsBr) with lithium aluminum hydride in ether or tetraglyme solution. Reaction of the primary or secondary arsine with GaMe 3 yielded a colorless, crystalline arsino(gallane) with empirical formula Me 2GaAs(H)Np or Me 2GaAsNp 2, respectively. The new compounds have been fully characterized according to elemental analysis, physical and solubility properties, IR, 1H and 13C NMR spectroscopies. Single crystal X-ray diffraction studies of Me 2GaAsNp 2 have shown the compound to be dimeric in the solid stare. The compound [Me 2GaAsNp 2] 2 crystallized in the triclinic space group P1 with unit cell parameters a=8.688(4), b=9.817(4), c=9.910(4) Å, V=774.7(6) Å 3 and Z=2. The planar (GaAs) 2 ring of the dimer lies on an inversion center with GaAs bond lengths of 2.529(1) and 2.532(1) Å. The endocyclic angles at As and Ga are 94.3(1) and 85.7(1)°, respectively.

ChemInform Abstract: Diastereoselective Synthesis of a Resolved Secondary Arsine Complex: Asymmetric Synthesis of (R)‐(‐)589‐Ethylmethylphenylarsine.

AbstractThe cyclopentadienyldicarbonyliron complex (I) is photochemically coupled with the chiral diphosphine (II), yielding the optically active complex (V) which reacts with the racemic arsine (±)‐(VI) under optical resolution to produce the chiral iron arsine complex (VII).

Diastereoselective synthesis of a resolved secondary arsine complex: asymmetric synthesis of ( R-(−) 589-ethylmethylphenylarsine

The reaction of [ R-( R ★, R ★)]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(NCMe)]PF 6 with (±)-AsHMePh in boiling methanol yields crystalline [ R-[( R ★)-( R ★, R ★)]-(+) 589)-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(AsHMePH) PF 6, optically pure, in ca. 90% yield, in a typical second-order asymmetric transformation. This complex contains the first resolved secondary arsine. Deprotonation of the secondary arsine complex with KOBu t at −65°C gives the diastereomerically pure tertiary arsenido-iron complex [ R-[( R ★),( R ★, R ★)]]-[((η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}FeAsMePh] · thf, from which optically pure [ R-[( S ★),( R ★, R ★)]]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(AsEtMePh)PF 6 is obtained by reaction with iodoethane. Cyanide displaces ( R)-(−) 589-ethylmethylphenylarsine from the iron complex, thereby effecting the asymmetric synthesis of a tertiary arsine, chiral at arsenic, from (±)-methylphenylarsine and an optically active transition metal auxiliary.

Reactions of (Me3SiCH2)2AsSiMe3 with gallium halides; crystal structure and dynamic NMR study of the dimer [[(Me3SiCH2)2As]2GaBr

Abstract : Prior to our recent studies, the only method of preparing organogallium-arsenic compounds was that reported by Coates et al. These authors prepared two mono (arsino) gallanes by the cleavage of a single Ga-C bond in Me3Ga with the As-H bond of a secondary arsine. In our hands, this reaction not only suffered a reduction in efficiency, but also eventually failed to yield the desired products as the substituents on Gallium and Arsenic increased in size. Moreover, the fact that bis-and tris (arsino) gallanes could not be made by this route led us to examine alternative methods of forming the Ga-As bond, viz., the coupling of gallium chlorides with lithium arsenides or silyl arsines. Others have since reported the use of the lithium arsenide method. There is ample precedent for the reaction of silyl substituted main-group elements (E-SiMe) with covalent halides MC1*, to yield an E-M bond and Me3SiCl.

Syntheses and Reactions of Arsenides, Stibides, and Bismuthides

This review deals with the synthesis and preparative uses of metallic derivatives of primary and secondary arsines, stibines, and bismuthines. Reaction of these derivatives (usually called arsenides, stibides, and bismuthides) with organic halides has become an important synthetic pathway to tertiary arsines, stibines, and bismuthines. They have also proved useful for the preparation of organic compounds containing covalent bonds between arsenic or antimony and silicon, germanium, tin, or lead. A number of secondary arsines have been obtained by the reaction of arsenides of the type RAsHNa with alkyl halides. 1. The Cleavage of Triarylarsines or Triarylstibines with Alkali Metals. 2. The Cleavage of Diarsines, Bis[diarylarsenic] Oxides, and Arseno Compounds. 3. The Reaction of Secondary Arsines and Stibines with Organolithium Compounds or with Alkali Metals. 4. The Reaction of Primary Arsines with Sodium or Potassium. 5. The Reaction of Primary Arsines with Organolithium Reagents. 6. Reactions in which Haloarsines, Halostibines, or Halobismuthines react with an Alkali Metal. 7. Reactions of the Alkali Metal Arsenides M3As and (M2As)2 and the Alkali Metal Stibides M3Sb and (M2Sb)2 with Alkyl Halides. 8. Miscellaneous Reactions.

Reactions of chloramine, dimethylchloramine, and chlorine with arsine, primary arsines, and secondary arsines

Reactions of chloramine, dimethylchloramine, and chlorine with arsine, primary arsines, and secondary arsines

The synthesis and properties of some organosilicon secondary arsines and a cyclic organosilicon arsine

The synthesis and properties of some organosilicon secondary arsines and a cyclic organosilicon arsine

Perfluoroalkyl arsenicals X. Some reactions of secondary arsines and diarsines with fluoroolefins

The secondary arsines (CH 3) RAsH (R = CH 3, C 6H 5) react with the fluoroolefins X C=X(CF 2) nC F 4 (X = Cl, F; n = 1, 2) to yield (CH 3)RAs C=CX(CF 2) nC F 2 with elimination of HX. (CH 3) 2As-As(CH 3) 2 and Cl C(CF 2) nC F 2 afford (CH 3) 2− As C=CCl(CF 2) nC F 2 with elimination of ClAs(CH 3) 2. (CH 3) 2AsMgBr reacts with CF 2=CFCF 3 and CF=CFCF 2C F 2 to give (CH 3) 2AsCF=CFCF 3 and (CH 3) 2As C=CFCF 2C F 2 respectively. (CH 3) 2AsCF 2CFHCF 3 is obtained from (CH 3) 2AsH and CF 3CF=CF 2.