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Synthesis and characterization of the samarium-cobalt complexes (C/sub 5/Me/sub 5/)/sub 2/(THE)SmCo(CO)/sub 4/ and (SmI/sub 2/(THF)/sub 5/)(Co(CO)/sub 4/): X-ray crystal structure of a seven-coordinate samarium(III) cation complex

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00220a038· OSTI ID:5956760
Co/sub 2/(CO)/sub 8/ reacts with the divalent samarium complexes (C/sub 5/Me/sub 5/)/sub 2/Sm(THF)/sub 2/ and SmI/sub 2/(THF)/sub x/ to form (C/sub 5/Me/sub 5/)/sub 2/(THF)SmCo(CO)/sub 4/ and (SmI/sub 2/(THF)/sub 5/)(Co(CO)/sub 4/), respectively. Co/sub 2/(CO)/sub 8/ reacts with ((C/sub 5/Me/sub 5/)SmI(THF)/sub 2/)/sub 2/ to form a complex that disproportionates to (C/sub 5/Me/sub 5/)/sub 2/(THF)SmCo(CO)/sub 4/ and (SmI/sub 2/(THF)/sub 5/)(Co(CO)/sub 4/). The latter complex crystallizes from THF in the triclinic space group P1 with unit cell dimensions a = 8.829 (4) A, b = 12.965 (4) A, c = 14.740 (5) A, ..cap alpha.. = 88.48 (3)/sup 0/, ..beta.. = 81.63 (3)/sup 0/, ..gamma.. = 87.51 (3)/sup 0/, and Z = 2 for D/sub calcd/ = 1.86 g cm/sup -3/. The complex exists as discrete SmI/sub 2/(THF)/sub 5//sup +/ cations and Co(CO)/sub 4//sup -/ anions with no Sm-O-Co isocarbonyl linkage. The coordination geometry around the samarium atom is roughly pentagonal bipyramidal with the iodide atoms at the two apical positions (Sm-I) distances 3.030 (2) and 3.009 (2) A). The Sm-O(THF) distances vary from 2.44 (1) to 2.47 (1) A. The Co(CO)/sub 4//sup -/ anion has a tetrahedral geometry. 41 references, 1 figure, 4 tables.
Research Organization:
Univ. of California, Irvine
OSTI ID:
5956760
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:26; ISSN INOCA
Country of Publication:
United States
Language:
English