Syntheses of Dinuclear Metal Complexes of Rhodium, Iridium, Iron, Molybdenum, and Cobalt with Novel Bridged 2,2‘-Bis(indenyl) Systems

Abstract

The first unsymmetric monosilanylene-bridged 2,2′-bis(indenyl) system, 1,1′-(2,2′-C 9 H 6 ) 2 -Si(Me)(t-Bu) (3c), was synthesized in the same manner as the disilanylene and disiloxanylene systems. Furthermore, a series of dinuclear complexes with these double-bridged ligands were reacted with appropriate metal fragments, yielding 1 10b) for cobalt. All compounds were obtained as the antifacial isomer, except complex 8a, where a mixture of the syn and anti species was obtained. The redox behavior of 8a was investigated by cyclic voltammetry in CH 2 Cl 2 . The structures of 6b and 8a were determined by X-ray diffractometry.

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 averages of these Fe-C bond lengths are 2.058 Å in 1 and meso-2, and 2.062 and 2.057 Å in rac-3. All these Fe-C distances are in good agreement with the respective values reported for (g 5 -4,7-dimethylindenyl)(g 5 -pentamethylcyclopentadienyl)iron(II) [21] and bis(g 5 -cyclopentadienyl)[1,1 0 -tetramethyldisiloxy-2,2 0 -bis(g 5 -indenyl)]diiron(II) [22] and also with those values found in substituted bis(g 5 -indenyl)iron(II) complexes [23]. The relatively large range of the Fe-C bond distances indicates that the g 5 -coordination towards the indenyl ligand is not perfect, but displays some extent of ene-allyl distortion and is hence better described as a g 3 + g 2 mode.…”

“…The averages are 2.055 Å in meso-4, and 2.063 and 2.054 Å in 5. These values are similar to those in 1, meso-2 and rac-3 and are also in good agreement with previously reported data [21,22].…”

Synthesis and reactivity of 2-(tert-butylcyclopentadienyl)-indenyl dinuclear ruthenium complex [η5:η5-(tBuC5H3)(C9H6)]Ru2(CO)4: Halogen induced Ru cleavage from indenyl ring

“…Synthesis and X-ray structure of [g 5 :g 5 -( t BuC 5 H 3 )(C 9 H 6 )]Ru 2 (CO) 4 Reaction of Ru 3 (CO) 12 with the unsymmetrical Fv ligand 2-(tertbutylcyclopentadienyl)-indene (1) in refluxing toluene afforded the normal Fv dinuclear ruthenium complex [g 5 :g 5 -( t BuC 5 H 3 ) (C 9 H 6 )]Ru 2 (CO) 4 (2) in good yield (Scheme 1). The reaction can be also conducted in heptane and xylene, just with relatively lower yields.…”

“…Later, Gaede and Tews demonstrated the synthesis of bridged dibenzofulvalene ligand and its Mo, Fe, Co, Rh, and Ir complexes [11,12]. However, the fulvalene ligands with unsymmetrical backbones, such as 2-(cyclopentadienyl)-indenyl species, were less explored.…”

“…In this study, we will report the synthesis of [g 5 :g 5 -( t BuC 5 H 3 ) (C 9 H 6 )]Ru 2 (CO) 4 (2) by reaction of 2-(tert-butylcyclopentadienyl)-indene (1) with Ru 3 (CO) 12 were recorded as KBr disks on a Nicolet 380 FT-IR spectrometer. Elemental analyses were performed on a Perkin-Elmer 240C analyzer.…”