η1-Indenyl derivatives of transition metal and main group elements: synthesis, characterization and molecular dynamics

Coordinatively Unsaturated Cationic and Zwitterionic [Cp*Ru(κ2‐P,N)] Complexes: Ligand‐Assisted Double‐Geminal CH Bond Activation and Reversible α‐H Elimination at Ruthenium

“…These observations are consistent with the mechanism outlined in Scheme ,11c in which the transiently formed zwitterion 7 undergoes an intramolecular CH activation process to yield a zwitterionic relative of 4 11d. Regioselective proton transfer from ruthenium to the indenide ligand backbone regenerates a coordinatively unsaturated alkylruthenium complex that undergoes a second CH activation step (α‐H elimination) to yield 8 a , which isomerizes to 8 b 13. The facile rearrangement of 7 to 8 b is remarkable, since double‐geminal CH bond activation to give a RuC complex is rare and invariably requires extended heating and loss of a small molecule to facilitate the reaction 12…”

Synthesis and properties of bis(indenyl) derivatives of ytterbium and lutetium. Molecular structures of the complexes (C9H7)2Ln(μ-Cl)2Li(Et2O)2 (Ln = Yb, Lu) and [(C9H7)2YbCl2][Li(DME)3]

“…However, as opposed to complexes 2 and 3, both chlorine atoms in complex 4 are involved in the formation of these contacts. One of chlorine atoms forms contacts simultaneously with two hydrogen atoms of the six membered rings of two indenyl ligands (Cl(1)...H (7) and Cl (1) …”

“…The THFhexane extracts were concentrated, and red crystals of (C 9 H 7 ) 2 Yb(THF) 2 were obtained (0.84 g, 61%). In the mother liquor, indene was detected by GLC in a yield of 0.45 g (52% 7 Li NMR (20 °C, pyridine d 5 ), δ: 6.5.…”

“…These characteristic features are associated with the coordination nonrigidity of the indenyl ligand, its tendency to undergo haptotropic rearrangements, and the ability to form metal-ligand bonds of different nature depending on the electronic configuration of the central atom. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Recently, we have synthesized the first f transition metal complex with the µ η 5 :η 4 bridging indenyl ligand, whose coordination to two ytterbium atoms gives rise to the dinuclear mixed valence (Yb II /Yb III ) complex. 18 In addition, when investigating the reaction of the ytterbium bis(indenyl) complex (C 9 H 7 ) 2 Yb(THF) 2 with 2 {[(2,6 diisopropylphenyl)imino]methyl}pyridine, we have dis covered 19 the unusual insertion of the N=C double bond at the Yb-C 9 H 7 η 5 bond.…”

Synthesis and structure of mono- and dinuclear cyclopentadienyl–indenyl complexes of iron(II) and further reactions to mixed tri- and tetranuclear iron–cobalt complexes

“…The reason for this enhanced reactivity, which is commonly referred to as indenyl effect, is generally attributed to a re-aromatization of the fused arene ring in the transition state. The chemistry of indenyl metal complexes has been summarized in several recent reviews [6][7][8]. The presence of two fused psystems in the indenyl system enables this bicyclic arene to act as a bridging ligand in homo-and heterobinuclear complexes [L n M(lg:g-ind)M 0 L 0 n ].…”