TY - JOUR
T1 - Syntheses and crystal structures of ruthenium and rhodium olefin complexes containing GaCp
AU - Cadenbach, Thomas
AU - Gemel, Christian
AU - Bollermann, Timo
AU - Fischer, Roland A.
PY - 2009/6/1
Y1 - 2009/6/1
N2 - The reactivity of olefin containing complexes of the d8 metals Ru0 and Rh1 toward GaCp* and AlCp * is presented. [Ru(η4-butadiene)(PPh 3)3] reacts with GaCp* to give the substitution product [Ru(η-butadiene)(PPh3)2(GaCp *)] (1), which proved to be stable in the presence of GaCp * even under hydrogenolytic conditions. In contrast, the bis-styrene complex [Ru(PPh3)2(styrene)2] undergoes full substitution of the olefin ligands to give [Ru(PPh 3)2(GaCp*)3] (2), whereas reaction of [RU(η2, η2-COD)(η6-COT) ] (COD = 1,5-cyclooctadiene, C8H12, COT = 1,3,5-cyclooctatriene, C8H10) and GaCp* leads to [Ru(η2,η2-COD)(GaCp*) 3] (3) under mild hydrogenolytic conditions. Analogously, the Rh 1 compounds [{Rh(η2,η2-NBD)(PCy 3)2}{BArF}] (NBD = norbornadiene) and [{Rh(η2,η2-COD)2}{BArF}] ({BArF}= B{[C6H3(CF3) 2]4) yield the complexes [{Rh(η2, η2-NBD)(PCy3)(GaCp*) 2}{BArF}] (4), [{Rh(η2,η2- COD)(GaCp*)3}{BArF}] (5), and [{Rh(η2,η2-COD)(AICp*) 3}{BArF]}] (6) upon reaction with the appropriate ECp * ligand (E = Al, Ga). All new complexes have been characterized by means of 1H and 13C NMR spectroscopy and elemental analysis, as well as X-ray single crystal structure analysis in the case of 1-5.
AB - The reactivity of olefin containing complexes of the d8 metals Ru0 and Rh1 toward GaCp* and AlCp * is presented. [Ru(η4-butadiene)(PPh 3)3] reacts with GaCp* to give the substitution product [Ru(η-butadiene)(PPh3)2(GaCp *)] (1), which proved to be stable in the presence of GaCp * even under hydrogenolytic conditions. In contrast, the bis-styrene complex [Ru(PPh3)2(styrene)2] undergoes full substitution of the olefin ligands to give [Ru(PPh 3)2(GaCp*)3] (2), whereas reaction of [RU(η2, η2-COD)(η6-COT) ] (COD = 1,5-cyclooctadiene, C8H12, COT = 1,3,5-cyclooctatriene, C8H10) and GaCp* leads to [Ru(η2,η2-COD)(GaCp*) 3] (3) under mild hydrogenolytic conditions. Analogously, the Rh 1 compounds [{Rh(η2,η2-NBD)(PCy 3)2}{BArF}] (NBD = norbornadiene) and [{Rh(η2,η2-COD)2}{BArF}] ({BArF}= B{[C6H3(CF3) 2]4) yield the complexes [{Rh(η2, η2-NBD)(PCy3)(GaCp*) 2}{BArF}] (4), [{Rh(η2,η2- COD)(GaCp*)3}{BArF}] (5), and [{Rh(η2,η2-COD)(AICp*) 3}{BArF]}] (6) upon reaction with the appropriate ECp * ligand (E = Al, Ga). All new complexes have been characterized by means of 1H and 13C NMR spectroscopy and elemental analysis, as well as X-ray single crystal structure analysis in the case of 1-5.
UR - http://www.scopus.com/inward/record.url?scp=66249094151&partnerID=8YFLogxK
U2 - 10.1021/ic802283r
DO - 10.1021/ic802283r
M3 - Artículo
C2 - 19400559
AN - SCOPUS:66249094151
SN - 0020-1669
VL - 48
SP - 5021
EP - 5026
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 11
ER -