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Synthesis, crystal structures and solution dynamics of some mono(2,4-dimethylpentadienyl)ruthenium(II) complexes

Lumini, Tito and Cox, David and Roulet, Raymond and Schenk, Kurt (1992) Synthesis, crystal structures and solution dynamics of some mono(2,4-dimethylpentadienyl)ruthenium(II) complexes. Journal of Organometallic Chemistry, 434 (3). pp. 363-385. ISSN 0022-328X

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Abstract

The reaction of [Ru(η5-C7H11)2H]BF4 (1; (η5-C7H11) = η5-2,4-dimethylpentadienyl (DMP)) with 2-electron or cyclic 6-electron ligands gives the salts [Ru(η5-C7H11)L3]BF4 (L  CO, PMe3, P(OMe)3, CH3CN; L3 = 1,1,1-tris(diphenylphosphinomethyl)ethane) and [Ru(η5-C7H11)(ηn-ring)]BF4 ((ηn-ring) = η6-cyclohepta-1,3,5-triene, η-cycloocta-1,3,5,7-tetraene, η6-arene, η5-thiophene). In the presence of a halide salt, 1 reacts with 4-electron diene ligands to give neutral [Ru(η5-C7H11)(diene)X] complexes (X  I, Cl, and (diene) = η4-buta-1,3-diene; η4-2,3-dimethylbuta-1,3-diene, η2:η2- cycloocta-1,5-diene) and with 2-electron ligands to give neutral [Ru(η2-C7H11)L2X] complexes (X  I, Br, Cl and L  CO, P(OMe)3, PMe3; X  I and L2 = bis(diphenylphosphino)ethane; X  Cl and L2 = N,N,N′,N′-tetramethylethylenediamine). [Ru(η5-C6H7)(η4-C 6H8)I] is the product of the reaction of 1 with cyclohexa-1,3-diene and KI. The complexes [Ru(η5-C7H11)(P(OMe)3)3]BF4 and [Ru(η5-C7H11)L2I] (LCO, P(OMe)3) have been crystallographically characterized. Complexes of the type [Ru(η5-C7H11)L3]+ and [Ru(η5-C7H11)L2X] exhibit dynamic behaviour in solution due to rotation of the DMP ligand with respect to the RuL3 or RuL2X groups, and activation energies for twelve of the complexes have been evaluated. Exchange of free and coordinated acetonitrile in solutions of [Ru(η5-C7H11)(NCCH3)3]BF4 is non-stereospecific and associative in character.

Item Type: Article
Journal or Publication Title: Journal of Organometallic Chemistry
Subjects:
Departments: Faculty of Science and Technology > Lancaster Environment Centre
ID Code: 64995
Deposited By: ep_importer_pure
Deposited On: 10 Jun 2013 11:00
Refereed?: Yes
Published?: Published
Last Modified: 30 Aug 2017 14:09
Identification Number:
URI: http://eprints.lancs.ac.uk/id/eprint/64995

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