Abstract
Photolyses of trans-Fe(CO)(3)(As((CH(2)) (n) )(3)As) (n = a, 10; b, 12; c, 14) in the presence of PMe(3), or reactions of trans-[Fe(CO)(2)(NO)(As((CH(2)) (n) )(3)As)](+) BF(4) (-) and n-Bu(4)N(+) Cl(-), afford the air stable title complexes As((CH(2)) (n) )(3)As (8a-c) in 79-34% yields. With 8a, the in, in and out, out isomers are separable and each is crystallographically characterized. With 8b,c, the isomers rapidly interconvert by homeomorphic isomerization, but each crystallizes (contrathermodynamically) as an out, out isomer. Reactions of 8c with H(2)O(2) or 8b with BH(3) give 8c·2O or 8b·2BH(3), respectively (85-94%). Reactions of 8c with MCl(2) (M = Pt, Pd, Ni), Rh(CO)(Cl), and Fe(CO)(3) sources afford the corresponding cage-like complexes trans-ML (n) (As((CH(2))(14))(3)As) (86-51%). The crystal structures of 8c·2O and the PtCl(2) and PdCl(2) adducts are determined and compared to those of 8a-c and diphosphorus analogs. The corresponding distibine Sb((CH(2))(14))(3)Sb is analogously prepared, but precursors necessary for the bismuth analog could not be accessed due to the diminished BiR(3) Lewis basicity.