Ap. Lyon et Dh. Macartney, KINETIC AND SPECTROSCOPIC STUDIES ON ALPHA-CYCLODEXTRIN ROTAXANES WITH PENTACYANO(CYANOPYRIDINIUM)FERRATE(II) STOPPERS, Inorganic chemistry, 36(4), 1997, pp. 729-736
[2]Pseudorotaxanes have been prepared by threading linear chains of th
e type [R(CH2)(n)R](2+) (where R=3- or 4-cyanopyridine and n=9 or 10)
through alpha-cyclodextrin (alpha-CD), and subsequently converted to t
he corresponding [2]rotaxane species by coordinating bulky [Fe(CN)(5)]
(3-) end groups. The lability of the iron(II)-cyanopyridinium bonds al
so permits the spontaneous rotaxane self-assembly upon cyclodextrin ad
dition to the iron dimer complexes. The mechanism for this process inv
olves the rate-determining dissociation of a [Fe(CN)(5)](3-) unit ((7/-1)x10(-2) s(-1) at 25 degrees C for [(NC)(5)Fe(4CNpyr(CH2)(9)4CNpyr)
Fe(CN)(5)](4-)). The stability constants for the alpha- and beta-CD in
clusion complexes; {AD-CNpyr . CD}(+) and [Fe(CN)(5){AD-CNpyr . CD}](2
-) (AD-CNpyr(+)=1-adamantan-1'-yl-3- and -4-cyanopyridinium), have bee
n determined by H-1 NMR spectroscopy and ligand substitution kinetic s
tudies. The rate constants for the ligand substitution reactions of th
e [Fe(CN)(5)(AD-CNpyr)](2-) and [Fe(CN)(5)(CNpyr(CH2)(n)CNpyr)](-) com
plexes exhibited significant diminutions in the presence of alpha- and
beta-CD, owing to inclusions of the free and coordinated cationic lig
ands.