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Synthesis and reactivity of cationic bis(N-heterocyclic dicarbene) ruthenium(II) complexes (Articolo in rivista)

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Synthesis and reactivity of cationic bis(N-heterocyclic dicarbene) ruthenium(II) complexes (Articolo in rivista) (literal)

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Tubaro C.; Bertinazzo D.; Monticelli M.; Saoncella O.; Volpe A.; Basato M.; Badocco D.; Pastore P.; Graiff C.; Venzo A. (2014)
Synthesis and reactivity of cationic bis(N-heterocyclic dicarbene) ruthenium(II) complexes
in European journal of inorganic chemistry (Print); Wiley-VCH Verlag Gmbh, Weinheim (Germania)
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Tubaro C.; Bertinazzo D.; Monticelli M.; Saoncella O.; Volpe A.; Basato M.; Badocco D.; Pastore P.; Graiff C.; Venzo A. (literal)

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http://onlinelibrary.wiley.com/doi/10.1002/ejic.201301583/abstract;jsessionid=7A7E640C0FD46DE8F2D4F3B43D7E5DBE.f04t01 (literal)

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1-8 : Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131 Padova, Italy / 9 : Dipartimento di Chimica, Università di Parma, Viale delle Scienze 17/A, 43100 Parma, Italy / 10 : IENI-CNR, Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131 Padova, Italy (literal)

Titolo

Synthesis and reactivity of cationic bis(N-heterocyclic dicarbene) ruthenium(II) complexes (literal)

Abstract

Four ruthenium(II) N-heterocyclic dicarbene complexes of general formula [Ru{MeIm(CH2)nImMe}2(RCN)2][PF6]2 (1: n=1,R=Me;2: n=1,R=Ph;3: n=2,R=Me;4: n=2,R=Ph; MeIm = 3-methylimidazol-2-yliden-1-yl) have been synthesised by transmetalation of the dicarbene ligand from a dicarbene silver complex with [RuCl2(COD)]x (COD = 1,5-cyclooctadiene) or [RuCl2(p-cymene)]2as ruthenium precursors. The relative position of the coordinated nitrile molecules (cisortrans) depends on the group that links the two carbene moieties: the dicarbene with the methylene bridge affords thetransisomer, whereas theciscomplex is obtained with the ethylene bridge. The lability of coordinated nitriles towards entering nucleophiles, in particular, cyclohexyl and tert-butyl isocyanide, has been carefully checked, and the corresponding substitution complexes [Ru{MeIm(CH2)nImMe}2(RNC)2][PF6]2(6: n=1,R=Cy;7: n=2,R=Cy;8: n=2,R=tBu) have been synthesised. The transcomplexes are more inert than thecisones, and benzonitrile is a better leaving group than acetonitrile; these characteristics allow a proper tuning of the coordination set and the stereoelectronic properties of these dicarbene ruthenium complexes. The Xray crystal structures of1and7have also been determined. (literal)

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