A Tale of Biphenyl and Terphenyl Substituents for Structurally Diverse Ketiminato Magnesium, Calcium and Germanium Complexes

Abstract

In this paper, we have used two N,O‐ketiminato ligands (L1 and L2) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe3)2 and subsequent reaction with MgI2 led to a homoleptic dinuclear magnesium complex (1) with a Mg2O2 four‐membered ring. Deprotonation with nBuLi and subsequent reaction with MgI2 afforded a unusual dinuclear magnesium complex (2) with a Mg2O2 ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex (3) with six four‐membered Ca2O2 rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium (4) and calcium (5) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride (7) with L1. However, with L2, an unusual ligand scrambling, and a C−C coupling take place, leading to the formation of a secondary carbocation with GeCl3‐ as a counter‐anion (8). Besides, a germanium dichloride adduct (9) bound to the oxygen center of the ligand was obtained as the minor product.

A Well‐Defined Calcium Compound Catalyzes Trimerization of Arylisocyanates into 1,3,5‐Triarylisocyanurates

“…We reasoned that such a ligand might be appropriate for the calcium atom, because it provides a high coordination number around the metal center, and thereby could hinder the formation of a homoleptic compound. [27,28] The reaction between LH and KN(TMS) 2 in THF led to a dimeric potassium complex (1) (Scheme 1). Lithiation of the ligand by MeLi, with the subsequent addition of CaI 2 , afforded a hexacoordinate calcium complex (2) (Scheme 1).…”

“…The ligand consists of a diaminoethane group as core and pyridine and di‐ tert ‐butyl‐phenolate as peripheral moieties. We reasoned that such a ligand might be appropriate for the calcium atom, because it provides a high coordination number around the metal center, and thereby could hinder the formation of a homoleptic compound [27,28] . The reaction between LH and KN(TMS) 2 in THF led to a dimeric potassium complex ( 1 ) (Scheme 1).…”