New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines

Abstract

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing "through-space" NMR spin-spin J couplings existing within several of these polyphosphines.

Synthesis, coordination studies and redox properties of a novel ditertiary phosphine bearing two ferrocenyl groups

“…Yield: 0.054 g, 86%. Selected data for 2: 31 P{ 1 (5) Compound 1 (0.011 g, 0.124 mmol) was added to a stirred solution of PdCl 2 (cod) (0.034 g, 0.117 mmol) in CH 2 Cl 2 (20 mL). The solution was stirred for 0.5 h and the solvent concentrated to ca.…”

“…The ferrocenyl (Fc) group continues to play a fundamental role in the design of new mono-and polyphosphorus containing ligands and some of their transition metal complexes have been studied as homogenous catalysts [1][2][3][4][5]. The versatility of the Fc group in synthesis can be illustrated by some of the diverse compounds (Chart 1) previously documented in the literature.…”

“Through-space” 31P spin–spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

“…We had provided a rationale to the coupling constants observed between the different phosphorus atoms, clearly demonstrated to be a result of nonbonded interactions [6]. In particular, based on a model developed by Mallory and co-workers [7], an expression of the nucleus distance-dependence of 31 P-31 P spin-spin couplings in coordination complexes has been given [6,8,9]. In the course of searches devoted to the electrochemistry of palladium halide tetraphosphine complexes, we synthesized a new palladium complex that had not been considered in our previous studies.…”

Hexaphosphine: A Multifaceted Ligand for Transition Metal Coordination

“…[1] As steric effects are crucial in the reactivity of metal-phosphane complexes, a good knowledge of the molecular structures of the species is required both in the solid state and in solution. [6][7][8][9][10][11][12][13][14][15][16][17][18] The performance of some of these branched polyphosphanes in catalysis, for instance, regarding C-C bond formation, [19,20] has driven progress in their synthesis. [6][7][8][9][10][11][12][13][14][15][16][17][18] The performance of some of these branched polyphosphanes in catalysis, for instance, regarding C-C bond formation, [19,20] has driven progress in their synthesis.…”