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Tuning Main Group Redox Chemistry through Steric Loading: Subvalent Group 13 Metal Complexes of Carbazolyl Ligands
Author(s) -
Mansaray Hassanatu B.,
Kelly Michael,
Vidovic Dragoslav,
Aldridge Simon
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003440
Subject(s) - steric effects , chemistry , homoleptic , ligand (biochemistry) , metal , disproportionation , isostructural , stereochemistry , coordination complex , crystallography , crystal structure , organic chemistry , catalysis , biochemistry , receptor
The ability of substituted carbazol‐9‐yl systems to ligate in σ fashion through the amido N‐donor, or to adopt alternative coordination modes through the π system of the central five‐membered ring, can be tuned by systematic variation in the steric demands of substituents in the 1‐ and 8‐positions. The differing affinities of the two modes of coordination for hard and soft metal centres can be shown to influence not only cation selectivity, but also the redox properties of the metal centre. Thus, the highly sterically sterically demanding 1,3,6,8‐tetra‐ tert ‐butylcarbazolyl ligand can be used to generate the structurally characterised amido‐indium(I) complex, [{( t Bu 4 carb)In} n ], (together with its isostructural thallium counterpart) in which the metal centre interacts with the central pyrrolyl ring in η 3 fashion [ d (InN)=2.679(3) Å; d (InC)=2.819(3), 2.899(3) Å]. By contrast, the smaller 3,6‐di‐ tert ‐butylcarbazolyl system is less able to restrict the metal centre from binding at the anionic nitrogen donor in the plane of the carbazolyl ligand (i.e. in σ fashion). Analogous chemistry with In I precursors therefore leads to disproportionation to the much harder In II [and In 0 ], and the formation of the mixed‐valence product, [In 2 {In 2 ( t Bu 2 carb) 6 }], a homoleptic molecular [In 4 (NR 2 ) 6 ] system. This chemistry reveals a flexibility of ligation for carbazolyl systems that contrasts markedly with that of the similarly sterically encumbered terphenyl ligand family.