ARCHITECTURE OF THE ORGANOMETALLIC ION-EXCHANGERS [(ME3SNIV)4MII(CN)6]INFINITY(M = FE, RU, OS) - A COMBINED MULTINUCLEAR SOLID-STATE MAGNETIC-RESONANCE AND INFRARED RAMAN-SPECTROSCOPIC STUDY
S. Eller et al., ARCHITECTURE OF THE ORGANOMETALLIC ION-EXCHANGERS [(ME3SNIV)4MII(CN)6]INFINITY(M = FE, RU, OS) - A COMBINED MULTINUCLEAR SOLID-STATE MAGNETIC-RESONANCE AND INFRARED RAMAN-SPECTROSCOPIC STUDY, Organometallics, 12(8), 1993, pp. 3232-3240
With extensive use of the N-15 isotopomer, 1a, of the organotin polyme
r [(Me3Sn)4Fe(CN)6]infinity (1) and of variable-temperature solid-stat
e C-13 NMR studies, the CP MAS C-13, N-15, and Sn-119 NMR spectra of t
he coordination polymers [(Me3SnIV)4MII(CN)6]infinity with M = Fe (1),
Ru (2), and Os (3) have been fully determined and optimally assessed.
According to these measurements, the asymmetric unit involves three e
qually-abundant, nonequivalent CN ligands and two equally-abundant, no
nequivalent Me3Sn groups with six crystallographically different methy
l C atoms. A structural model is proposed in which one type of N atom
is bonded to two Sn atoms. Below -20-degrees-C, each of the six CH3 gr
oups gives rise to an individual, sharp 13C signal, while above room t
emperature rapid rotation of both Me3Sn groups leads to two resonances
. The vibrational spectra in the nu(SnC) and nu(CN) absorption ranges
suggest the exclusive presence of trigonal planar Me3Sn fragments and
one significantly distorted (from O(h)), albeit still centrosymmetric,
M(CN)6 unit (local symmetry: D4h from IR/Ra: D2h from NMR). From all
spectroscopic findings, a three-dimensional network reminiscent of tha
t of the polymeric acid [H4Fe(CN)6]infinity may be deduced. The prefer
red architecture, which also involves three-coordinate cyanide N atoms
, -CNSn2, contrasts with the known structures of polymeric [(R3Sn)2CO3
]infinity systems wherein both penta- and tetracoordinated Sn atoms co
exist.