TY - JOUR
T1 - The first oxygen-bridged diorganoarsenic(V) compound: the crystal structure of AsMe2(S)OAs(S)Me-2
AU - Silaghi-Dumitrescu, L
AU - Pascu, Sofia
AU - Silaghi-Dumitrescu, I
AU - Haiduc, I
AU - Gibbons, M N
AU - Sowerby, D B
PY - 1997
Y1 - 1997
N2 - The oxidation of tetramethyldiarsinedisulfide, (AsMe2S)(2), with t-BuOOH under anhydrous conditions leads to both AsMe2(S)-S-As(O)Me-2 1 and AsMe2(S)-O-As(S)Me-2 2. The formation of the oxygen-bridged isomer 2 is unexpected and can he rationalised as resulting from either oxidation of the As(III)/As(III) form of the disulfide, (AsMe2-S-S-AsMe2), or by an oxotropic rearrangement of 1 via a cyclic As2OS transition state. RHF/3-21G* ab initio calculations predict that the ore-bridged species 2 is more stable than the thio-bridged form 1. The molecular structure of 2 has been determined by single crystal X-ray diffraction.
AB - The oxidation of tetramethyldiarsinedisulfide, (AsMe2S)(2), with t-BuOOH under anhydrous conditions leads to both AsMe2(S)-S-As(O)Me-2 1 and AsMe2(S)-O-As(S)Me-2 2. The formation of the oxygen-bridged isomer 2 is unexpected and can he rationalised as resulting from either oxidation of the As(III)/As(III) form of the disulfide, (AsMe2-S-S-AsMe2), or by an oxotropic rearrangement of 1 via a cyclic As2OS transition state. RHF/3-21G* ab initio calculations predict that the ore-bridged species 2 is more stable than the thio-bridged form 1. The molecular structure of 2 has been determined by single crystal X-ray diffraction.
UR - http://dx.doi.org/10.1016/s0022-328x(97)00500-7
U2 - 10.1016/s0022-328x(97)00500-7
DO - 10.1016/s0022-328x(97)00500-7
M3 - Article
SN - 0022-328X
VL - 549
SP - 187
EP - 192
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -