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Graphical Abstract: Eur. J. Inorg. Chem. 12/2010
Publication year - 2010
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.201090033
Subject(s) - chemistry , carbene , ligand (biochemistry) , nucleophile , ruthenium , electrophile , hydride , transition metal , stereochemistry , reactivity (psychology) , metal , osmium , medicinal chemistry , crystallography , catalysis , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
The cover picture shows various reactions of the carbene complex [Ru(η 5 ‐C 5 Me 5 ){κ 2 ‐ P , N ‐P i Pr 2 NHC 5 H 4 N}(=CHC 6 H 5 )] + over a view of Cádiz (phoenician Gadir), one of the oldest european continuously inhabited cities. These processes illustrate its ambiphilic character. It reacts as a nucleophile with Br?nsted acids, yielding a complex with an η 2 ‐benzyl ligand. There are some previously described examples of this coordination mode for early transition metal benzylidene complexes, but this represents the first example of a structural characterization in the case of ruthenium complexes. The electrophilic behaviour of [Ru(η 5 ‐C 5 Me 5 ){κ 2 ‐ P , N ‐P i Pr 2 NHC 5 H 4 N}(=CHC 6 H 5 )] + has been shown by reaction with hydride, giving rise to an η 1 ‐benzyl complex. Normally, NMR studies allow unambiguous characterization of the η 1 coordination of a benzyl ligand. However, especially for late transition metal complexes, distinction between the usually disregarded η 2 and the generally considered η 3 mode is difficult. We propose, from this study, that the presence of an η 2 ‐benzyl ligand in metal complexes should not be ruled out only on the basis of their NMR spectra. The carbene complex also reacts with other bases like KO t Bu, KN(SiMe 3 ) 2 and PMe 3 . Details are discussed in the article by I. Macías‐Arce, M. C. Puerta and P. Valerga on p. 1767 ff.