Hydrogenation of Olefins Catalyzed by a Cobalt(I) Hydride Complex with N‐Heterocyclic Silylene

Jia, Hongwei; Du, Shaozhi; Xu, Chuangchuang; Mo, Zhenbo

doi:10.1002/ejic.202300086

Cited by 4 publications

(1 citation statement)

References 69 publications

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“…The latter was further converted to the hydrido analogue Co-73-H in the presence of s Bu 3 BHK (Scheme 54). 148 Both NHSi-Co complexes were fully characterized and engaged in the hydrogenation of olefins, where the hydrido complex showed better activity (Scheme 54a). It is worth mentioning that a total chemoselectivity toward the alkene was observed when using an unsaturated carbonyl compound, which is quite rare in cobalt chemistry (Scheme 54b).…”

Section: N X Cobalt Complexes (N = 1−4)mentioning

confidence: 99%

Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview

Bories,

Sodreau,

Barbazanges

et al. 2024

Organometallics

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For decades, transition-metal catalysts based on noble metals have proven to be highly efficient for a wide range of organic transformations. However, due to their low abundance and highly volatile price the use of such metals is now critical for the economy. Thus, the use of more sustainable alternatives is mandatory and the more abundant first-row transition metals are becoming interesting challengers. Among them low-valent 3d transition metals appeared as the best candidates, as they are intrinsically more reactive than highvalent ones. However, this reactivity implies that these complexes are often generated in situ, putting further away the aspect of atom economy and low waste. To circumvent this and to get more insight on the mechanism of reaction, the concept of well-defined complexes has emerged. In this area, due to its historic development and the trouble associated with the preparation of other well-defined 3d transitionmetal complexes, cobalt appears as an important player. In this review, after a definition of what is a low-valent complex and the presentation of the concept of a well-defined (pre)catalyst also known as the "single-component" strategy we will report the syntheses and applications in catalysis of low-valent well-defined cobalt complexes classified by their oxidation state and ligand environment.

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Section: N X Cobalt Complexes (N = 1−4)mentioning

confidence: 99%

Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview

Bories,

Sodreau,

Barbazanges

et al. 2024

Organometallics

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Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes

Cabeza,

García‐Álvarez

2024

Chemistry A European J

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This review article focuses on amidinatotetrylenes that potentially can (or have already shown to) behave as bi‐ or tridentate ligands because they contain at least one amidinatotetrylene moiety (silylene, germylene or stannylene) and one (or more) additional coordinable fragment(s). Currently, they are being widely used as ligands in coordination chemistry, small molecule activation and catalysis. This review classifies those that have been isolated as transition metal‐free compounds into five families that differ in the position(s) of the donor group(s) (D) on the amidinatotetrylene moiety, namely: ED{R1NC(R2)NR1}, EX{DNC(R2)NR1}, EX{R1NC(D)NR1}, EX{DNC(R2)ND} and E{R1NC(R2)ND}2 (E = Si, Ge or Sn). Those that do not exist as transition metal‐free compounds but have been observed as ligands in transition metal complexes are cyclometallated and ring‐opened amidinatotetrylene ligands. This article presents schematic descriptions of their structures, the approaches used for their syntheses and a quick overview of their involvement (as ligands) in transition metal‐catalysed reactions. The literature is covered up to the end of 2023.

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Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Alonso,

Cabeza,

García-Álvarez

et al. 2024

Inorg. Chem.

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E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N′-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom oscillates from being attached to the two amidinate N atoms to being chelated by an amidinate N atom and its closest quinolyl N atom (both situations are similarly stable according to density functional theory calculations). The hmds group of 1a and 1b is still reactive and the deprotonation of another equivalent of Hbqfam can be achieved, allowing the formation of the homoleptic derivatives E(bqfam)2 (E = Ge, Sn). The reactions of 1a and 1b with [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod = cycloocta-1,5-diene), [Ru3(CO)12] and [Co2(CO)8] have been investigated. The gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] (E = Ge, Sn) have a monodentate κE-tetrylene ligand and display fluxional behavior in solution the same as that of 1a and 1b. However, the palladium(II) and platinum(II) complexes [MCl{κ3 E,N,N′ -ECl(hmds)(bqfam)}] (M = Pd, Pt; E = Ge, Sn) contain a κ3 E,N,N′-chloridotetryl ligand that arises from the insertion of the tetrylene E atom into an M–Cl bond and the coordination of an amidinate N atom and its closest quinolyl N atom to the metal center. Finally, the binuclear ruthenium(0) and cobalt(0) complexes [Ru2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(CO)6] and [Co2{μE-κ3 E,N,N′ -E(hmds)(bqfam)}(μ-CO)(CO)4] (E = Ge, Sn) have a related κ3 E,N,N′ -tetrylene ligand that bridges two metal atoms through the E atom. For the κ3 E,N,N′-metal complexes, the quinolyl fragment not attached to the metal is pendant in all the germanium compounds but, for the tin derivatives, is attached to (in the Pd and Pt complexes) or may interact with (in the Ru2 and Co2 complexes) the tin atom.

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Hydrogenation of Olefins Catalyzed by a Cobalt(I) Hydride Complex with N‐Heterocyclic Silylene

Cited by 4 publications

References 69 publications

Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview

Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview

Polydentate Amidinato‐Silylenes, ‐Germylenes and ‐Stannylenes

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

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