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Synthesis and Structural Properties of Anhydrous Rare Earth Cinnamates, [ RE (cinn) 3 ]
Author(s) -
Deacon Glen B.,
Forsyth Craig M.,
Junk Peter C.,
Hilder Matthias,
Leary Stuart G.,
Bromant Claudia,
Pantenburg Ingo,
Meyer Gerd,
Skelton Brian W.,
White Allan H.
Publication year - 2008
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700359
Subject(s) - cinnamates , anhydrous , chemistry , crystal structure , crystallography , cinnamic acid , metal , lanthanide , polymer chemistry , organic chemistry , ion
Abstract Anhydrous rare earth tris(cinnamates) [ RE (cinn) 3 ] ( RE = La–Lu, Y and Sc and cinnH = trans ‐cinnamic acid) were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5‐tetramethylbenzene flux at ca. 200 °C. X‐ray crystal structure determinations and X‐ray powder data show that, in the solid state, the larger lanthanoids (La–Dy) form an isomorphous polymeric series consisting of homoleptic nine‐coordinate metal centres bonded to three chelating and bridging tridentate cinnamates. The late RE III cinnamate ( RE = Dy, Ho–Lu, Y) complexes also form linear one‐dimensional polymeric chains with all RE metal atoms being seven‐coordinate. The cinnamates are either bound tridentate bridging in a μ‐η 2 :η 1 fashion, or μ‐η 1 :η 1 syn‐syn bidentate bridging. A structural break occurs at dysprosium which has been characterised in both crystallographic forms, and gives solely the late RE form when precipitated at 80 °C. Sc III cinnamate was also isolated as an analytically pure precipitate which was, again, found to be anhydrous in nature. A structural change was identified by powder XRD between the late RE III cinnamates and Sc III cinnamate.