Magnesium, calcium and zinc [N₂N′] heteroscorpionate complexes

Abstract

A series of Group 2 and 12 heteroscorpionate complexes is reported.

Four-Coordinate Fe N2 and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand

“…All reagents were purchased from commercial suppliers and used without further purification unless otherwise noted. HC( t Bu pz) 2 SiMe 2 Cl, 25 (C 5 Me 4 (SiMe 3 )) 2 Ti, 26 and AdN 3 27 were prepared according to literature procedures.…”

Calcium Amido Complexes Coordinated by Tridentate Amidinate Ligands: Synthesis, Structures and Catalytic Activity in Olefin Hydrophosphination and Polymerization of Cyclic Esters

“…Two past decades are marked by significant advances in the synthesis of organic derivatives of alkaline earth elements and investigation of their structures and reactivity which resulted in the discovery of formerly unexpected rich catalytic potential of these compounds The increasing interest in the application of alkaline earth metal complexes in homogeneous catalysis is inspired by their non‐toxicity, low cost and prevalence of these elements in the earth′s crust . Thus, calcium amido complexes have been used as catalysts (or precatalysts) for ring‐opening polymerization (ROP) of cyclic ethers,, Tishchenko′s reaction, hydroamination‐cyclization, hydroamination,, hydrosilylation, hydroboration,, hydrophosphination, hydrophosphorylation of aldehydes and ketones, hydrogenation of activated alkenes, reactions of dehydrocoupling of amines with silanes,, dehydrocoupling of aminoboranes …”

Metalation of Aryl‐bis(3‐alkyl‐5‐methylpyrazol‐1‐yl)‐ methane (Alkyl=Me, Ad; Aryl=Ph, C6H4‐2−OH) with NaN(SiMe3)2, KN(SiMe3)2, and Ca{N(SiMe3)2}2

“…Alternatively, substitution of one pyrazolyl moiety by bulky silyl (R= t Bu, R*=SiMe 2 ‐NR’) [11] or phosphanyl groups (R=Me, R*=PPh 2 ‐NR’), [12] containing Lewis basic amido side‐arms, also stabilizes heteroleptic calcium complexes of the type [{(Me 3 Si) 2 N}Ca{C(Pz R2 ) 2 R*}].…”

“…Replacement of one pyrazolyl subunit by a phenyl group, leading to phenylbis(pyrazol-1-yl)methane (bis(pyrazolyl)methylbenzene), allows delocalization of the anionic charge (Scheme 2) and hence, reduces the nucleophilic character of the anionic methanide site. [10] Alternatively, substitution of one pyrazolyl moiety by bulky silyl (R = tBu, R* = SiMe 2 -NR') [11] or phosphanyl groups (R=Me, R*=PPh 2 -NR'), [12] containing Lewis basic amido side-arms, also stabilizes heteroleptic calcium complexes of the type [{(Me 3 Si) 2 N}Ca{C(Pz R2 ) 2 R*}].…”