Macrobicyclic Dibridgehead Di(trialkyl)pnictogens E((CH2)n)3E (E/n = As/10, As/12, As/14, Sb/14) and Their Cage-like Metal Complexes: Syntheses, Structures, and Homeomorphic Isomerizations
Samuel R. Zarcone, Peter J. Verardi, Gong M. Chu, Nattamai Bhuvanesh and John A. Gladysz*,
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引用次数: 0
Abstract
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–, afford the 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 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 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 corresponding cage-like complexes trans-MLn(As((CH2)14)3As) (86–51%). The crystal structures of 8c·2O and the PtCl2 and PdCl2 adducts are determined and compared to those of 8a–c and diphosphorus analogs. The corresponding distibine Sb((CH2)14)3Sb is analogously prepared, but precursors necessary for the bismuth analog could not be accessed due to the diminished BiR3 Lewis basicity.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.