Synthesis and X-ray crystal structures of hypervalent arsenic compounds bearing arsenic-iron bonds

Synthesis and Characterization of Antiapicophilic Arsoranes and Related Compounds

“…The C1− As1−C2 angle of 4b−Na•MeOH•3H 2 O (107.37°) is expanded by 6.5°compared with that of the CF 3 analog 4a−Et 4 N (100.9°) reported by our group. 75 This is in good agreement with the trend observed for analogous 10-Sb-4 compounds in which the corresponding angles are 110.3°for the C 2 F 5 derivative 67 and 103.6°for the CF 3 derivative. 66 This should be due to steric repulsion between the endo-C 2 F 5 group and the equatorial aromatic ring of the other bidentate.…”

“…Arsines 2, along with hydroxyarsoranes 3 and arsoranides 4, were prepared by treatment of AsCl 3 with 2-fold amounts of the corresponding bidentate ligands 1 (Scheme 1). 75 Compound 2a showed four distinct fluorine signals corresponding to the CF 3 groups in the 19 analogue which exists as a pentacoordinate hydrophosphorane with an equatorial P−H bond. 76,77 Although 2a was stable to air, 2b and 2c were gradually oxidized in the open air to give the corresponding hydroxyarsoranes 3b and 3c, respectively.…”

“…Arsines 2 , along with hydroxyarsoranes 3 and arsoranides 4 , were prepared by treatment of AsCl 3 with 2-fold amounts of the corresponding bidentate ligands 1 (Scheme ) . Compound 2a showed four distinct fluorine signals corresponding to the CF 3 groups in the 19 F NMR spectrum (δ = −73.7, −73.9, −76.2, and −77.2 ppm at 25 °C), and the two aromatic rings were equivalently observed by 1 H NMR.…”

“…The arsoranides 4 were easily separated from 2 by recrystallization ( n -hexane) or TLC ( n -hexane/CH 2 Cl 2 ) . Compound 4a-Li bearing the Martin ligand ( A ) was very stable to water or air, but 4b – Na and 4c–Na showed instability and slowly gave 3b and 3c , respectively.…”

Robust Structure and Reactivity of Aqueous Arsenous Acid–Platinum(II) Anticancer Complexes

“…In 1 and 2 , arsenic retains a formal oxidation state of three, and displays distorted TBP geometry with a PtO 4 coordination sphere. The TBP geometry around As III in metal complexes is uncommon, however it has been observed in complexes of an organoarsenic ligand with Pt II[15] and in complexes of Ag I[16] and Fe II 17. While As III can act as either a Lewis base or a Lewis acid,18 in 1 and 2 As III acts simultaneously as a Lewis base (As→Pt) and as a Lewis acid (O→As).…”