ISSN:
0009-2940
Keywords:
Ruthenium clusters
;
Azoalkane ligands
;
Hydrazine-derived ligands
;
Interconversions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Interconversions Between Ru3-Bound Azoalkane and Dialkylhydrazine-Derived Building UnitsReactions involving hydrogen transfer have been investigated starting from the azoalkane-bridged clusters Ru3(CO)9-(RCH2N≡NCH2R) (1a, R = H; 1b, R = Me). In boiling toluene they are isomerized to the hydrazonide-bridged clusters HRu3(CO)9(RCH2N - N≡CHR) (2a, R = H; 2b, R = Me). Pd/C-catalyzed hydrogenation converts both compound types into the hydrazide-bridged clusters HRu3(CO)9(RCH2N - NHCH2R) (3a, R = H; 3b, R = Me). Hydride attachment to 1 and 2 and deprotonation of 3 yield a common anionic intermediate 4 which is converted into 3 upon protonation. While deuteration experiments and NMR spectra indicate that the anionic intermediate equilibrates between the N - H and Ru - H isomers, aurations of deprotonated clusters with Ph3PAuCl yield the Ru - Au-connected clusters Ph3PAuRu3(CO)9(EtN - N≡CHMe) (5) and Ph3PAuRu3(CO)9(MeN - NHMe) (6). The reversible cluster expansion of 2b with Fe(CO)3 fragments which results in the formation of FeRu3(CO)12(μ4-η2-N2Et2) (7) involves a reversible reconversion of the hydrazonide ligand to the azoalkane ligand.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260907
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