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Synthesis and properties of the dichloro [tetramethyl (trifluoromethyl)cyclopentadienyl]ruthenium dimer: X-ray structure of [M2(η-C5Me4CF3)2Cl2(μ-Cl)2] (M=Ru, Rh) |
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| Authors: | Oleg V. Gusev Mikhail A. Ievlev Konstantin A. Lyssenko Pavel V. Petrovskii Nikolai A. Ustynyuk Peter M. Maitlis |
| Affiliation: | a A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 117813, Moscow, Russia b Department of Chemisty, The University of Sheffield, S3 7HF, Sheffield, UK |
| Abstract: | The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru2(η5-C5Me1CF2)2 (μ-Cl2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2J=200 cm1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh2(η5-C5Me4CF3(2Cl2(μ-Cl)2] (3) (rhombohedral system. space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η5-C5Me4CF4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2(μ-Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the η5-C5ME5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2(η5-C5Me4CF3)2Br2 (μ-Br2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric η6-fulvene dimers [Ru2(η6-C5Me3CF3 = CH2)2Cl2(μ-Cl)2] (5). Reactions of 5 with CO and allyl chloride give Ru(η5-C5Me3CF3CH2Cl)(CO)2Cl (6) and Ru(η5-C5Me3CF3CF3CH2Cl)(η3-C3H5)Cl2 (7) respectively. |
| Keywords: | Crystal structures Ruthenium complexes Trifluoromethyl complexes Fulvene complexes Cyclopentadienyl complexes |
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