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Monocyclooctatetraenyl(dithiolene)uranium Compounds
Author(s) -
Arliguie Thérèse,
Thuéry Pierre,
Fourmigué Marc,
Ephritikhine Michel
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400403
Subject(s) - chemistry , crystallography , protonation , hexamethylphosphoramide , crystal structure , ligand (biochemistry) , stereochemistry , metal , medicinal chemistry , ion , organic chemistry , biochemistry , receptor
Abstract The neutral mononuclear dithiolene compounds [U(cot)(dithiolene)(tppo) 2 ] [cot = η‐C 8 H 8 ; dithiolene = dddt ( 9 ), dmio ( 10 ), mdt ( 11 )], [U(cot)(dithiolene)(hmpa) 2 ] [dithiolene = dddt ( 12 ), dmio ( 13 ), mdt ( 14 )], [U(cot)(mdt)(bipy)] ( 15 ) and [U(cot)(mdt)(terpy)] ( 16 ) were obtained by treating the dimeric complexes [{U(cot)(dithiolene)} 2 ] [dithiolene = dddt ( 3 ), dmio ( 4 ), mdt ( 5 )] (dddt = 5,6‐dihydro‐1,4‐dithiine‐2,3‐dithiolate; dmio = 1,3‐dithiole‐2‐one‐4,5‐dithiolate; mdt = 1,3‐dithiole‐4,5‐dithiolate) with the corresponding Lewis base [triphenylphosphine oxide (tppo), hexamethylphosphoramide (hmpa), 2,2′‐bipyridine (bipy), or 2,2′:6′,2′′‐terpyridine (terpy)]. Complexes 9· 2THF, 11· 2THF, 12 , 13 , 14 , 15 and 16· 1.5py have been crystallographically characterized. The crystal structures show a significant interaction between the C=C double bond of the dithiolene ligand and the metal centre. The 1 H NMR spectra reveal the fluxional behaviour of the compounds in solution in relation to the facile inversion of the dithiolene ring. The variation of the activation energies of the inversion process reflects the steric congestion of the complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)