The exchange reaction of tetramethyl-diphosphine, -diarsine, -distibine and -dibismuthine

Abstract

Tetramethyldiphosphine and tetramethyldiarsine undergo an exchange reaction to give (dimethylarsino)dimethylphosphine.The equilibrium constant at 25°C in benzene is found to be 0.26. Similarly, mixtures of tetramethyldistibine with tetramethyldiarsine or tetramethyldibismuthine are partially converted to (dimethylarsino)dimethylstibine or (dimethylbismuthino)dimethylstibine, respectively. The thermochromic arsinostibine, l-(2,5-dimethylarsolo)-2,5_dimethylstibole, has been prepared by a similar reaction.

A review on completing arsenic biogeochemical cycle: Microbial volatilization of arsines in environment

“…Volatile As-S and As-Cl compounds have been synthesized in the laboratory as early as in 1980s (Ashe and Ludwig, 1986;Tesfalidet and Irgum, 1988). It has been known that arsine can form volatile chloroarsine (AsCl 3 ) when in contact with HCl vapor.…”

Bismuthanylstibanes

“…16,17 This unusual gap is likely due to the kinetic lability of neutral Bi-Sb bonds -solution phase spectroscopic studies revealed that Ph2BiSbMe2 and Me2BiSbMe2 undergo rapid scrambling in solution to give combinations of dipnictanes at ambient temperature, precluding isolation of the heterobimetallic species. 18 The introduction of molecular charge has nevertheless enabled characterization of four charged compounds exhibiting Bi-Sb interactions (Scheme 1): the [SbBi3Br9] 3cluster anion (B), 19 the polymeric ribbon of [BiSb2] 4-(C) found in the network solid Ba2BiSb2, 20 and the molecular cations [Ph3SbBiCl2] + (D) and [Ph3SbBiCl] 2+ (E). 21 .…”

“…The lone pair sites on each of the metallic atoms are oriented in opposite directions along the a-axis achieving maximum spatial distance between the two distinct naphthalenediamine ligand frameworks. Due to the similarity of the silyl groups present, a Bi/Sb substitutional disorder was detected in To assess the stability of the Bi-Sb bonds, a sealed sample of Me BiSb Et was heated to 100 o C C6D6 for 72 h. No decomposition or redistribution was observed over this period, despite Me BiBi Me and Et SbSb Et being isolable compounds,8,22 in contrast to the aforementioned facile redistribution involving alkyl/aryl-substituted Bi-Sb bonds 18. To explore the specific influence of the bis(silylamino)naphthalene framework, we performed DFT calculations on Me BiSb Et , Ph2BiSbPh2, and (Me2N)2BiSb(NMe2)2.…”

Arsenic Compounds

“…Unlike many distibines and dibismuthines, diarsines do not appear to exhibit thermochromic effects (71). Although the preparation of diarsenes, the arsenic analogues of azo compounds, was first claimed during the nineteenth century, it was not until 1983 that such a compound was unequivocally characterized (72).…”