Isolation and Crystallographic Characterization of Allylindium Species Generated from Allyl Halide and Indium(0)

• Published in: European Journal of Organic Chemistry Vol. 2009; no. 32; pp. 5513 - 5517
• Main Authors: Yasuda, Makoto, Haga, Masahiko, Baba, Akio
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.11.2009; WILEY‐VCH Verlag; Wiley-VCH
• Subjects: Allylation; Chemical reactivity; Chemistry; Coordination compounds; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Indium; Inorganic chemistry and origins of life; N ligands; Noncondensed benzenic compounds; Organic chemistry; Preparations and properties; Reactive intermediates; Reactivity and mechanisms; X-ray analysis; Reaction intermediate; Complexation; Nitrogen heterocycle; Ligand; Organic bromine compounds; Indium; Ketone; X ray diffraction; Allylic compound; Organic halogen compounds; Allylation; Indium bromide; Pyridine derivatives; Characterization; N ligands; Indium Organic compounds; Pyridine; Reactive intermediates; Cinnamic acid derivatives; Benzenic compound; X-ray analysis; Lewis base; Chemical reactivity; Crystalline structure
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200900955

The reaction of cinnamyl bromide with indium(0) gave two allylindium species, cinnamylindium dibromide and dicinnamylindium bromide. Either species were isolated after complexation of appropriate pyridine‐type Lewis bases. The use of 3,5‐dibromopyridine (Br2py) as a Lewis base gave cinnamylindium dibromide with two Br2py ligands. Dicinnamylindium bromide was isolated with 4‐(dimethylamino)pyridine (Me2Npy) ligands. In both cases, the indium atom showed a trigonal‐bipyramidal coordination sphere with the cinnamyl group(s) and bomine atom(s) in equatorial and the pyridine‐type ligands in axial positions. The cinnamylindium bromide transformed to dicinnamylindium bromide with formation of InBr3 in the presence of Me2Npy. The dicinnamylindium bromide had a higher reactivity than the monoallyl compound for carbonyl addition.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Allylindium was isolated from allyl halide and indium(0). The reaction of cinnamyl bromide with indium gave two allylindium species, cinnamylindium dibromide and dicinnamylindium bromide. Either species were isolated after complexation of pyridine‐type Lewis bases and analyzed by X‐ray crystallography. Their reactivity was also investigated.