TY - JOUR
T1 - Synthetic, structural and computational studies on adducts of the 4,1,2-SnC2B10 supraicosahedral stannacarborane
AU - Abram, Peter D.
AU - McKay, David
AU - Ellis, David
AU - Macgregor, Stuart A.
AU - Rosair, Georgina M.
AU - Welch, Alan J.
PY - 2010
Y1 - 2010
N2 - The stannacarborane 1,2-µ-(CH2)3-4,1,2-closo- SnC2B10H10 (1) and its adducts with 2,2'-bipyridine (bipy), 1,10-phenanthroline (o-phen) and 4,4'-diphenyl-2,2'-bipyridine (Ph2bipy), 1,2-µ-(CH2)3-4-(bipy)-4,1,2-closo-SnC2B 10H10 (2), 1,2-µ-(CH2)3-4-(o- phen)-4,1,2-closo-SnC2B10H10 (3) and 1,2-µ-(CH2)3-4-(Ph2bipy)-4,1,2-closo- SnC2B10H10 (4), respectively, together with the analogous compound 1,2-µ-{C6H4(CH2) 2}-4-(bipy)-4,1,2-closo-SnC2B10H10 (5) have been prepared and characterised. In solution at ambient temperature, compounds 1-5 all display NMR spectra which are interpreted in terms of (time-averaged) Cs molecular symmetry, but whilst (effectively) Cs symmetry is retained in the structures of 2-5 in the crystal (i.e. henicosahedral cage structures are observed), 1 has a (C1-symmetric) docosahedral structure. A method for quantifying the "percentage docosahedral character" of 13-vertex 1,2-C2 heteroboranes is described, based on the angles around the C1C2B9B5 quadrilateral. The structures of "carbons adjacent"1-5 all reveal less slipping of the Sn atom (or {SnL2} fragment) across the C2B4 carborane face than has previously been observed in analogous "carbons apart" 4,1,6-closo-SnC2B10 species, a surprising result in the context of previous studies of slipping in icosahedral platinacarboranes. A computational study of "carbons adjacent" and "carbons apart" icosahedral and supraicosahedral platinacarboranes has revealed that the origin of this observation is steric control of the slipping distortion in both "carbons apart" species and in the "carbons adjacent" 13-vertex species, with orbital interactions proving dominant only in the case of the "carbons adjacent" icosahedral compound. © The Royal Society of Chemistry 2010.
AB - The stannacarborane 1,2-µ-(CH2)3-4,1,2-closo- SnC2B10H10 (1) and its adducts with 2,2'-bipyridine (bipy), 1,10-phenanthroline (o-phen) and 4,4'-diphenyl-2,2'-bipyridine (Ph2bipy), 1,2-µ-(CH2)3-4-(bipy)-4,1,2-closo-SnC2B 10H10 (2), 1,2-µ-(CH2)3-4-(o- phen)-4,1,2-closo-SnC2B10H10 (3) and 1,2-µ-(CH2)3-4-(Ph2bipy)-4,1,2-closo- SnC2B10H10 (4), respectively, together with the analogous compound 1,2-µ-{C6H4(CH2) 2}-4-(bipy)-4,1,2-closo-SnC2B10H10 (5) have been prepared and characterised. In solution at ambient temperature, compounds 1-5 all display NMR spectra which are interpreted in terms of (time-averaged) Cs molecular symmetry, but whilst (effectively) Cs symmetry is retained in the structures of 2-5 in the crystal (i.e. henicosahedral cage structures are observed), 1 has a (C1-symmetric) docosahedral structure. A method for quantifying the "percentage docosahedral character" of 13-vertex 1,2-C2 heteroboranes is described, based on the angles around the C1C2B9B5 quadrilateral. The structures of "carbons adjacent"1-5 all reveal less slipping of the Sn atom (or {SnL2} fragment) across the C2B4 carborane face than has previously been observed in analogous "carbons apart" 4,1,6-closo-SnC2B10 species, a surprising result in the context of previous studies of slipping in icosahedral platinacarboranes. A computational study of "carbons adjacent" and "carbons apart" icosahedral and supraicosahedral platinacarboranes has revealed that the origin of this observation is steric control of the slipping distortion in both "carbons apart" species and in the "carbons adjacent" 13-vertex species, with orbital interactions proving dominant only in the case of the "carbons adjacent" icosahedral compound. © The Royal Society of Chemistry 2010.
UR - http://www.scopus.com/inward/record.url?scp=77149150914&partnerID=8YFLogxK
U2 - 10.1039/b922644c
DO - 10.1039/b922644c
M3 - Article
C2 - 20162216
SN - 1477-9226
VL - 39
SP - 2412
EP - 2422
JO - Dalton Transactions
JF - Dalton Transactions
IS - 9
ER -