Chiral Dirhodium(II) Carboxylates: New Insights into the Effect of Ligand Stereo-Purity on Catalyst Structure and Enantioselectivity

Adly, Frady G.; Bollard, Hannah; Gardiner, Michael G.; Ghanem, Ashraf

doi:10.3390/catal8070268

“…While many transition metal catalysts have been demonstrated to be effective in C−H insertion reactions, dirhodium paddlewheel complexes have been established as a privileged class of catalysts (see Figure 5). [11–16] …”

Section: Introductionmentioning

confidence: 99%

“…While many transition metal catalysts have been demonstrated to be effective in CÀHi nsertion reactions,d irhodium paddlewheel complexes have been established as ap rivileged class of catalysts (see Figure 5). [11][12][13][14][15][16] Catalytic reactions via carbene intermediates often employ diazo compounds as precursors to metal carbenes.T hese intermediates can be isolated in some cases or generated in situ;w hen exposed to ac atalyst, nitrogen gas is extruded and the metal carbene is formed. In most cases of acceptor-substituted carbenes,d iazo transfer to as tabilized anion affords the carbene precursor.F or donor-substituted carbenes,d iazo compounds are typically generated from hydrazone precursors (Figure 3).…”

Section: Introductionmentioning

confidence: 99%

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Bergstrom

¹

,

Nickerson

²

,

Shaw

³

et al. 2020

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Donor/donor carbenes are relatively new in the field of carbene chemistry; although applications in C−H and X−H insertion reactions are few in number, they demonstrate exquisite chemo‐ and stereo‐selectivity. Recent reports have shown that C−H, N−H, B−H, O−H, S−H, Si−H, Ge−H, Sn−H and P−H insertion reactions are feasible with a variety of transition metal catalysts, both inter‐ and intramolecularly. Furthermore, high degrees of diastereo‐ and enantioselectivity have been observed in several cases. Methods typically involve the formation of a diazo‐based carbene precursor, but procedures using diazo‐free metal carbenes have been developed with significant success. This Minireview covers transition‐metal catalyzed insertion reactions with donor/donor and donor carbenes, providing context for future developments in this emerging field.

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“…Moreover, dirhodium units have been used to form one-dimensional coordination compounds using bridging ligands between the dimetallic cores [18][19][20][21]. The use of other metal complexes as connectors between the paddlewheel units can lead to the formation of heterometallic one-dimensional coordination polymers, whose versatile chemical and physical properties, such as temperature dependent luminescence or modulation of their electronic structures, make those polymers promising materials [22][23][24][25]. An interesting approach to obtain this kind of heterometallic one-dimensional polymers is the use of platinum complexes to form {[Rh 2 ]-[Pt 2 ]-[Pt 2 ]} n chains, in which the different dimetallic units show direct Rh-Pt metal-metal bonds [26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Prior

¹

,

Cortijo

²

,

González‐Prieto

³

et al. 2019

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In this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.

show abstract

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Bergstrom

¹

,

Nickerson

²

,

Shaw

³

et al. 2020

View full text Add to dashboard Cite

Donor/donor carbenes are relatively new in the field of carbene chemistry; although applications in C−H and X−H insertion reactions are few in number, they demonstrate exquisite chemo‐ and stereo‐selectivity. Recent reports have shown that C−H, N−H, B−H, O−H, S−H, Si−H, Ge−H, Sn−H and P−H insertion reactions are feasible with a variety of transition metal catalysts, both inter‐ and intramolecularly. Furthermore, high degrees of diastereo‐ and enantioselectivity have been observed in several cases. Methods typically involve the formation of a diazo‐based carbene precursor, but procedures using diazo‐free metal carbenes have been developed with significant success. This Minireview covers transition‐metal catalyzed insertion reactions with donor/donor and donor carbenes, providing context for future developments in this emerging field.

show abstract

Chiral Dirhodium(II) Carboxylates: New Insights into the Effect of Ligand Stereo-Purity on Catalyst Structure and Enantioselectivity

Cited by 6 publications

References 63 publications

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

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