Zinc‐Catalyzed Reductions of Unsaturated Compounds

Metal–Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes

“…With respect to utilizing molecular main group metal complexes for catalytic transformations, one common impediment is redox innocence, often nullifying their ability to undergo the fundamental organometallic reactions of oxidative addition and reductive elimination (Figure ). , For example, in homogeneous zinc, magnesium, and calcium catalyzed reactions, the metal is almost exclusively limited to the M 2+ oxidation state, and thus productive cycles depend on only sigma bond metathesis and/or insertion steps which do not alter the oxidation state of the metal. , Nonetheless, utilizing this paradigm, complexes of these metals and other main group metals have demonstrated versatile catalytic applications including hydroamination, polymerization, hydrosilylation, − hydroboration, and hydrogenation − in which metal hydride intermediates are often speculated (and occasionally isolated). − Zinc, in particular, has shown activity for all of these transformations and is a promising metal due to its low cost, relatively high abundance, and low toxicity. ,, …”

“… 18 − 20 Zinc, in particular, has shown activity for all of these transformations and is a promising metal due to its low cost, relatively high abundance, and low toxicity. 2 , 21 , 22 …”

Zinc Hydride-Catalyzed Hydrofuntionalization of Ketones

“…As far as zinc-catalyzed hydrofunctionalization of carbonyls is concerned, there are reports on zinc-catalyzed hydrosilylation of carbonyls . Mainly, Parkin et al, Nikonov et al, Okuda et al, Rivard et al, Jones et al, Mösch-Zanetti et al, and Venugopal et al independently reported zinc hydride-catalyzed hydrosilylation of ketones (Figure A–G).…”

Cationic Zinc Hydride Catalyzed Carbon Dioxide Reduction to Formate: Deciphering Elementary Reactions, Isolation of Intermediates, and Computational Investigations

“…Molecular zinc compounds have received prominence as reagents for the reduction of unsaturated bonds [1–4] . They are employed in the reduction of olefins, [5–8] imines, [9–11] aldehydes, ketones, [12–18] and carbon dioxide [19–30] .…”

“…Molecular zinc compounds have received prominence as reagents for the reduction of unsaturated bonds. [1][2][3][4] They are employedi nt he reduction of olefins, [5][6][7][8] imines, [9][10][11] aldehydes, ketones, [12][13][14][15][16][17][18] and carbond ioxide. [19][20][21][22][23][24][25][26][27][28][29][30] Catalyticr eductiono f carbon dioxide through catalytic hydrosilylation [31][32][33][34] and, to some extent, hydroboration [35,36] with zinc catalysts has been investigated.…”