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Magnetic isomers of iron(II). Bis(C-cyanotrihydroborate)bis(phenanthroline)iron: a spin triplet

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50173a028· OSTI ID:7091738
The synthesis of an unusual six-coordinated, spin triplet (S = 1) ferrous complex, Fe(phen)/sub 2/(NCBH/sub 3/)/sub 2/, with cis geometry is described. This complex is characterized by its magnetic moment and infrared, visible-region, and Moessbauer spectra. On the basis of these data and the angular overlap model of metal--ligand bonding, -NCBH/sub 3/ is characterized as a ligand possessing moderate sigma- and pi-donor characteristics toward Fe(phen)/sub 2//sup 2 +/. How a proper balance of sigma- and pi-donor properties of -NCBH/sub 3/ and phen yields the spin-triplet state of the ferrous complex is discussed. Consideration of the CN stretching frequency data for the isomeric pairs of Fe(phen)/sub 2/(NCBH/sub 3/)/sub 2/ and Fe(phen)/sub 2/(CNBH/sub 3/)/sub 2/ and other bridged cyano species raises interesting questions about the effect of double coordination of cyanide on the CN sigma bonding. Finally, thermal stability studies of the Fe--CN--BH/sub 3/ and Fe--NC--BH/sub 3/ linkages eliminate the possibility of isomerization by a facile CN flip mechanism within the Fe and B cage and suggest that (phen)/sub 2/Fe(NCBH/sub 3/)/sub 2/ is the thermodynamically favored isomer.
Research Organization:
Kansas State Univ., Manhattan
OSTI ID:
7091738
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 16:7; ISSN INOCA
Country of Publication:
United States
Language:
English