C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon-boron bond into a carbon-X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row d-block transition metals have become increasingly widely used as catalysts for the formation of a carbon-boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon-boron bonds.

First-Row d-Block Element-Catalyzed Carbon-Boron Bond Formation and Related Processes.

Lanthanides and actinides : Annual survey of their organometallic chemistry covering the year 2000

The chemistry of actinide (An) and rare-earth metal (Ln and group 3) complexes featuring multiple bonding interactions with main-group fragments has witnessed an enormous growth since the first mentioning in the mid-eighties and apparent stagnation in the nineties. The recent surge of interest is particularly owing to our eagerness to acquire a fundamental understanding of the chemical bonding properties of such long-time elusive compounds but also the potential emergence of unprecedented reactivity in organic or inorganic transformations. Contrary to uranium imide chemistry, traditional and routine synthesis protocols seem less viable for rare-earth metal imide complexes. The present review puts its main emphasis on identifying reaction pathways currently available/elaborated for the generation of [An[double bond, length as m-dash]NR] and [Ln[double bond, length as m-dash]NR] moieties. We also address the intriguing structural and reactivity features of such organoimide derivatives as highlighted by small-molecule activation, group-transfer capability, and the redox chemistry of uranium, cerium, ytterbium, samarium and europium.

Rare-earth metal and actinide organoimide chemistry

This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e., geminal dianions, stabilized by main group elements. Three cases can thus be considered: the geminal-dilithio derivative, for which the two substituents at C are neutral, the yldiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review, the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications.

/pdf/geminal-dianions-stabilized-by-main-group-elements-bmn6wux3i0.pdf

Geminal Dianions Stabilized by Main Group Elements

Reactivity of Scandium Terminal Imido Complex toward Boranes: C(sp3)–H Bond Borylation and B–O Bond Cleavage

Lanthanide-based single-molecule magnets (Ln-SMMs) have become the most conspicuous SMMs exhibiting the highest effective barrier (Ueff) and blocking temperature (TB). Different strategies have been proposed to construct high-performance SMMs, including...

Low-coordinate Bis(imidazolin-2-iminato) Dysprosium(III) Single-Molecule Magnets

A series of monomeric rare-earth metal silyl-thiophosphinoyl-alkylidene complexes [LLn{C(SiR3 )PPh2 S}] (5: Ln=Lu, R=Me; 6: Ln=Lu, R=Ph; 7: Ln=Y, R=Me; 8: Ln=Y, R=Ph; 9: Ln=Sm, R=Ph; 10: Ln=Sm, R=Me; 11: Ln=La, R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH2 CH2 N(Me)2 )]- , DIPP=2,6-(iPr)2 C6 H3 ) have been synthesized and structurally characterized The influences of rare-earth metal ions, ancillary ligands, and alkylidene groups on the reactivity of complexes 5-11 and the related scandium complexes [LSc{C(SiR3 )PPh2 S}] (1: R=Me; 2: R=Ph) and [L'Sc{C(SiR3 )PPh2 S}] (3: R=Me; 4: R=Ph; L'=[MeC(NDIPP)CHC(Me)(NCH2 CH2 N(iPr)2 )]- ) have been studied Reactions of these rare-earth metal alkylidene complexes with PhCN give four kinds of products, the formation of which is dependent on the rare-earth metal ions, ancillary ligands, and alkylidene groups of the complexes In the reactions with tBuNC, unusual C-P bond cleavage of the alkylidene group and C≡C triple bond formation occur Complexes 10 and 11 also react with PhSiH3 to form hydrides, which subsequently undergo Ln-H addition to the C=N bond of the ancillary ligand L DFT calculations have been used to analyze the bonding in complex 10, which exhibits a polarized three centers Sm-C-P π interaction, and to rationalize the reactivity by computing reaction mechanisms The difference in reactivity of PhCN and tBuNC is due to the electron density delocalization that is enabled by the phenyl group rather than the tBu group

Monomeric Rare-Earth Metal Silyl-Thiophosphinoyl-Alkylidene Complexes: Synthesis, Structure, and Reactivity.

Approaching the uniaxiality of magnetic anisotropy in single-molecule magnets

The first non-pincer-type mononuclear scandium alkylidene complexes were synthesized and structurally characterized. These complexes exhibited short Sc-C bond lengths and even one of the shortest reported to date (2.1134(18) A). The multiple character of the Sc-C bond was highlighted by a DFT calculation. This was confirmed by experimental reactivity study where the complex underwent [2+1] cycloaddition with elemental selenium and [2+2] cycloaddition with imine. DFT calculation also revealed a strong nucleophilic behavior of the alkylidene complex that was experimentally demonstrated by the C-H bond activation of phenylacetylene.

Non-Pincer-Type Mononuclear Scandium Alkylidene Complexes: Synthesis, Bonding, and Reactivity.

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