A solvated zinc analogue of the calomel-dication

Abstract

The synthesis and characterisation of the solvent-stabilized salt [Zn2(THF)6](2+)[BAr4(F)]2(-) (1) is presented, which features the dizinc dication [Zn2](2+) as an analogue of the calomel dication [Hg2](2+). The labile tetrahydrofuran (THF) solvate molecules of 1 can be readily substituted by other ligands. Reaction with the strong donor ligand PMe3 (Me = CH3) leads to the Zn(ii) complex [Zn(PMe3)4](2+)[BAr4(F)]2(-) by disproportionation, while the π-acceptor-ligand phenylisocyanide (PhNC) gives the substitution product [Zn2(PhNC)6](2+)[BAr4(F)]2(-) (2) with an intact Zn-Zn bond.

Anomalous orbital admixture in ammine complexes

“…The change in PR 3 pyramidalization on coordination, slight as it is, has some implications for the important Tolman cone angles, so useful in making sense of steric effects of ligands. 27,28 M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 2 compound is square-planar at Cd, 33 but the Cd-O(THF) distances are long, so that the molecule is close to a 2-coordinated Cd(II) complex with weakly coordinated bases.…”

“…Phosphine (PH 3 ) complexes are uncommon, but PR 3 ligands are a workhorse of coordination and organometallic chemistry. [2][3][4][5][6] The ammine (NH 3 ) complexes are common, especially the Zn ones, and a typical structure of these complexes is shown in Fig. 1.…”

Atompräzise organometallische Zinkcluster

“…Bei Verwendung des weicheren t BuNC‐Liganden erfolgt hingegen eine direkte Koordination an den Clusterkern und die anschließende Entfernung labil gebundener ZnR‐Spezies. Diese Ergebnisse sind in Übereinstimmung mit unseren früheren Studien zur Reaktivität von [Zn 2 (THF) 6 ][BAr 4 F ] 2 gegenüber Isonitrilen, bei der die höhere Affinität des weicheren RNC‐Liganden (R= t Bu oder Ph) eine leichte Substitution der THF‐Moleküle durch Isonitrile an den Zn‐Zentren erlaubt …”

1,8‐Bis(borylamido)naphthalene Complexes of Lithium and Zinc(II) Including a Zinc(II) Isocyanide Adduct

“…Zinc(II) isocyanide adducts are of interest because they could serve as models for intermediates in zinc‐catalyzed processes involving isocyanides , . However, structurally authenticated zinc(II) isocyanide complexes are rare and include Zn(SeC 6 H 2 ‐2,4,6‐ t Bu 3 ) 2 (CN t Bu) 2 , ZnBr 2 (CN t Bu) 2 , {[HB(3,5‐(CF 3 ) 2 Pz) 3 ]Zn(CN t Bu) 3 }[B(3,5‐(CF 3 ) 2 C 6 H 3 ) 4 ], {[HB(3,5‐(CF 3 ) 2 Pz) 3 ]Zn(CN t Bu) 2 }[B(3,5‐(CF 3 ) 2 C 6 H 3 ) 4 ] (Pz = pyrazolyl), [Zn 2 (CNPh) 6 ][B{C 6 H 3 (CF 3 ) 2 } 4 ] 2 , and the 1,2,4,3‐triazaborol‐3‐yl ([TAB]) complex of zinc, {[TAB]ZnX(CNPh)} 2 (X = Cl and Br) …”