An Unprecedented Hybrid Scorpionate/Cyclopentadienyl Ligand

Abstract

An efficient method for the preparation of the first hybrid scorpionate/cyclopentadienyllithium compound as a new class of tridentate ligand is described. This compound is an excellent reagent for the introduction of this ligand into transition metal complexes.

Recent Advances in the Design and Coordination Chemistry of Heteroscorpionate Ligands Bearing Stereogenic Centres

“…This class of ligand was first described by us [15] and we have developed a well-established synthetic methodology to prepare a wide variety of these Having prepared this new class of hybrid scorpionate/ cyclopentadienyl precursors we explored their potential utility as tridentate ligands in the preparation of new group-4 metal complexes. [15] Thus Scheme 22). These processes gave complexes in yields of up to 90 %.…”

“…[14] The synthesis of hybrid chiral scorpionate/cyclopentadienyl ligands by a simple one-pot procedure has also been described. [15] Thus, deprotonation at the methylene group of bdmpzm followed by reaction with 6-tert-butylfulvene [16] yielded a chiral lithium compound in good yield (ca. 85 %) (see Scheme 9).…”

Synthesis and structural characterization of fluorenyltris(pyrazol-1-yl)borate ligands as new examples of cyclopentadienyl/scorpionate hybrid ligands

“…As first example of a related class of ligands, the cyclopentadienyl/bis(pyrazol-1-yl)methane system [Li 1-diphenylethylcyclopentadienyl] was described by Otero, Fernández-Baeza and co-workers [12] early in 2004. Even more recently, Marques and co-workers [13] have published the tetramethylcyclopentadienyl functionalized scorpionate [(C 5 Me 4 H)B(pz 3-Me ) 3 ] À while our group has reported on the fluorenyl-based ligand [FlBpz 3 ] À [14] (Fl: 9-fluorenyl).…”

Reactivity of Cyclopentadienes Modified by Bis(3,5‐dimethylpyrazol‐1‐yl)methyl Group to W(CO)5THF

“…Recently, Otero and co-workers successfully prepared the hybrid heteroscorpionate/cyclopentadienyl ligands by the reaction of fulvenes with bis(3,5-dimethylpyrazol-1-yl)methyllithium. 7 The potential utility of these ligands as valuable scaffolds in organometallic chemistry is being explored. A series of groups 3 and 4 metal complexes containing these hybrid heteroscorpionate/cyclopentadienyl ligands have been synthesized, 8,9 in which these ligands usually show a k 2 -N,N-η 5 -Cp coordination mode.…”