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Photolyses of trans-Fe(CO)3(As((CH2)n)3As) (n =a, 10; b, 12; c, 14) in the presence of PMe3, or reactions of trans-[Fe(CO)2(NO)(As((CH2)n)3As)]+ BF4− and n-Bu4N+ Cl−, affordthe air stable title complexes As((CH2)n)3As (8a−c) in 79−34%yields. With 8a, the in, in and out, out isomers are separable andeach is crystallographically characterized. With 8b,c, the isomersrapidly interconvert by homeomorphic isomerization, but eachcrystallizes (contrathermodynamically) as an out, out isomer.Reactions of 8c with H2O2 or 8b with BH3 give 8c·2O or 8b·2BH3,respectively (85−94%). Reactions of 8c with MCl2 (M = Pt, Pd,Ni), Rh(CO)(Cl), and Fe(CO)3 sources afford the correspondingcage-like complexes trans-MLn(As((CH2)14)3As) (86−51%). Thecrystal structures of 8c·2O and the PtCl2 and PdCl2 adducts are determined and compared to those of 8a−c and diphosphorusanalogs. The corresponding distibine Sb((CH2)14)3Sb is analogously prepared, but precursors necessary for the bismuth analogcould not be accessed due to the diminished BiR3 Lewis basicity 

Reactions of trans-[[upper bond 1 start]Fe(CO)2(NO)(As((CH2)n)3As[upper bond 1 end])]+ BF4− (n = 10, 12, 14) and Bu4N+ Cl− afford the title compounds As((CH2)n)3As, which upon reaction (n = 14) with MCl2 (M = Pt, Ni), Rh(CO)(Cl), and Fe(CO)3 sources reconstitute cage like complexes trans-[upper bond 1 start]MLn(As((CH2)14)3A[upper bond 1 end]s). Reactions with H2O2 and BH3 give the corresponding arsine oxides and boranes. Crystal structures of metal-free species reveal out,out isomers, but cage complex formation is proposed to entail homeomorphic isomerization to in,in isomers with endo directed lone pairs.