Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

“… 7 Like carbon, silicon generally has a valency of four, but lacks carbon’s ability to form double or triple bonds under mild conditions. 8 Silicon can also form hypervalent species, bonding to five—or even six—other atoms. Perhaps the most important difference between carbon and silicon is the ease with which the former forms long chains of the same element, known as catenation.…”

Section: Introductionmentioning

confidence: 99%

Biocatalytic Transformations of Silicon—the Other Group 14 Element

et al. 2021

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Significant inroads have been made using biocatalysts to perform new-to-nature reactions with high selectivity and efficiency. Meanwhile, advances in organosilicon chemistry have led to rich sets of reactions holding great synthetic value. Merging biocatalysis and silicon chemistry could yield new methods for the preparation of valuable organosilicon molecules as well as the degradation and valorization of undesired ones. Despite silicon’s importance in the biosphere for its role in plant and diatom construction, it is not known to be incorporated into any primary or secondary metabolites. Enzymes have been found that act on silicon-containing molecules, but only a few are known to act directly on silicon centers. Protein engineering and evolution has and could continue to enable enzymes to catalyze useful organosilicon transformations, complementing and expanding upon current synthetic methods. The role of silicon in biology and the enzymes that act on silicon-containing molecules are reviewed to set the stage for a discussion of where biocatalysis and organosilicon chemistry may intersect.

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“…Many reports and reviews have already been published describing how main group elements have emulated transition metals in terms of reactivity. [24][25][26][27][28][29][30][31] There are plethora of examples on FLPs (frustrated Lewis pairs) [32][33][34][35][36][37] and Nheterocyclic carbenes [38][39][40][41][42][43] being explored as homogeneous catalysts, but no dedicated review is available for the utilization of tetrylenes as catalysts in organic transformations.In this review we will cover the catalytic efficiency of compounds with heavier group 14 elements in + II oxidation state, which includes heavier tetrylenes and cationic species of Si(II), Ge(II), Sn(II). We have also compared the catalytic efficiency of these species (+ II) with the catalysts in + IV oxidation state for the same organic transformation.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, the study of low valent main group compounds as efficient catalysts will not only enrich the field of organometallic chemistry but will also provide a cheaper surrogates of nobel transition metals. Many reports and reviews have already been published describing how main group elements have emulated transition metals in terms of reactivity [24–31] . There are plethora of examples on FLPs (frustrated Lewis pairs) [32–37] and N‐heterocyclic carbenes [38–43] being explored as homogeneous catalysts, but no dedicated review is available for the utilization of tetrylenes as catalysts in organic transformations.In this review we will cover the catalytic efficiency of compounds with heavier group 14 elements in +II oxidation state, which includes heavier tetrylenes and cationic species of Si(II), Ge(II), Sn(II).…”

Section: Introductionmentioning

confidence: 99%

Heavier Tetrylenes as Single Site Catalysts

Sen

Khan

2021

Chemistry An Asian Journal

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An overview of the development of compounds with heavier low-valent group 14 elements (known as tetrylenes) as single component catalyst for organic transformation has been provided. Compounds with heavier group 14 elements possess stereochemically active lone pairs and energetically accessible π-antibonding orbitals, thereby resembling the electronic configuration of transition-metal compounds. Such compounds with low-valent group 14 elements has been known for small molecule activation since Power's report of dihydrogen activation by a digermyne, but their utilization in catalysis remained as a "Holy Grail" in main group chemistry. In recent years, numerous methodologies have been discovered epitomizing the use of Si(II), Ge(II) and Sn(II) compounds as single site catalysts for hydroboration of aldehydes, ketones, pyridines, cyanosilylation of aldehydes and ketones, N-formylations aromatic amines, dehydrocoupling reactions. This mini-review highlights these significant developments with an emphasis on the mechanistic investigation.

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Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

Abstract: Since the first heavy alkene analogues of germanium and tin were isolated in 1976, followed by West’s disilene in 1981, the chemistry of stable group 14 dimetallenes and dimetallynes advanced...

Cited by 105 publications

References 140 publications

How metallylenes activate small molecules

How metallylenes activate small molecules

Biocatalytic Transformations of Silicon—the Other Group 14 Element

Heavier Tetrylenes as Single Site Catalysts

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