Electronic and steric properties of stable silylene ligands in metal(0) carbonyl complexes

Reactivity of Diaminogermylenes with Ruthenium Carbonyl: Ru3Ge3 and RuGe2 Derivatives

“…(Scheme 1), 13 i.e., using a 6-fold excess of the NHM in THF at room temperature, resulted in no reaction at all. The large volume of this NHGe ligand and the previous observation that, for complexes with NHM ligands, the strength of metal−M bond decreases on going down in group-14, 5c,5f,14 seem to account for this result.…”

“…The NMR spectra of compound 2 confirm that the approximate C 3h symmetry found for this complex in the solid state is maintained in solution. Thus, the 13 to the empty p-orbital of the Ge atom that lowers the π-accepting capacity of these ligands. 5f,14…”

“…7 This intense NHC research activity has also included transition metal clusters, 8-10 on which NHCs are prone to undergo multiple C-H and C-N bond activation processes that cannot occur in mononuclear complexes. 8g-8j,10 To date, the transition metal chemistry of NHMs has been developed to a considerable extent, 4,5,[11][12][13] but, in general, reactivity 5f,11 and catalytic 12 studies on their complexes are scarce. Regarding transition metal clusters and NHMs, as far as we are aware, only one work has been hitherto reported.…”

“…Regarding transition metal clusters and NHMs, as far as we are aware, only one work has been hitherto reported. 13 It describes that the reaction of [Ru 3 (CO) 12 ] with a six-fold excess of 1,3-bis(tert-butyl)-2-silaimidazol-2-ylidene results in the formation of the mononuclear species [Ru{Si(N t Bu) 2 C 2 H 2 } 2 (CO) 3 ] (1, Scheme 1). 13 [Ru 3 (CO) In this paper, we report the reactivity of [Ru 3 (CO) 12 ] with two cyclic and one acyclic diaminogermylenes.…”

“…13 It describes that the reaction of [Ru 3 (CO) 12 ] with a six-fold excess of 1,3-bis(tert-butyl)-2-silaimidazol-2-ylidene results in the formation of the mononuclear species [Ru{Si(N t Bu) 2 C 2 H 2 } 2 (CO) 3 ] (1, Scheme 1). 13 [Ru 3 (CO) In this paper, we report the reactivity of [Ru 3 (CO) 12 ] with two cyclic and one acyclic diaminogermylenes. In addition to unveiling the synthesis of the first diaminogermylene derivatives of ruthenium, including an Ru 3 Ge 3 cluster that is the first transition metal cluster containing an NHM ligand of any kind, we also show that the nuclearity of the products of the reactions of [Ru 3 (CO) 12 ] with diaminogermylenes strongly depends upon the volume and the cyclic or acyclic structure of the latter.…”