A Zinc Carboxylate Network Containing Metal Sites with Low Coordination Numbers

Abstract

A bifunctional m-terphenyl, 2,6-diphenyl-1,4-dibenzoic acid (Ph2BDC), was synthesized and used in the preparation of a 2-D metal-organic coordination polymer. The steric hindrance of the bulky bifunctional linker forces low coordination at the Lewis-acidic zinc center. A zinc carboxylate dimer was prepared as a model compound to examine the unusual tricoordinate geometry at the metal site.

Metal-dependent dimensionality in coordination polymers of a semi-rigid dicarboxylate ligand with additional amide groups: Syntheses, structures and luminescent properties

“…5). The distance of four Zn-O bonds (1.939(2) to 1.951(2) Å) and the O-Zn-O bond angles (98.70 (15) to 115.10(10)°), are close to those of the reported [52,53].…”

Alkylzinc Carboxylates as Efficient Precursors for Zinc Oxocarboxylates and Sulfidocarboxylates

“…[4] Our experience in the design, synthesis, and structural characterization of organozinc complexes as models for various transformations [6] prompted us to explore whether alkylzinc carboxylates [7] can be used to synthesize alkoxyzinc carboxylates and other potentially useful clusters. [4] Our experience in the design, synthesis, and structural characterization of organozinc complexes as models for various transformations [6] prompted us to explore whether alkylzinc carboxylates [7] can be used to synthesize alkoxyzinc carboxylates and other potentially useful clusters.…”

“…The most common synthetic routes for the preparation of extended framework structures with zinc carboxylates as SBUs are based on solvothermal methods and involve inorganic zinc salts as substrates. [4] Our experience in the design, synthesis, and structural characterization of organozinc complexes as models for various transformations [6] prompted us to explore whether alkylzinc carboxylates [7] can be used to synthesize alkoxyzinc carboxylates and other potentially useful clusters. Herein, we present the synthesis and characterization of the novel alkylzinc carboxylate cluster [EtZn(O 2 CPh)] 6 (1) as well as its reactions with dioxygen and elemental sulfur as a new efficient route to zinc oxocarboxylates and sulfidocarboxylates.…”

Conversion between Doubly and Triply Carboxylate Bridged Bis(ethylzinc) Complexes and Formation of the (μ-Oxo)tetrazinc Carboxylate [Zn4O(ArTolCO2)6]

“…From THF, a dizinc complex, [Zn 2 (PhCO 2 ) 3 (Et)(THF)] ( 12 ), 9 crystallizes, with a ratio of 3:1. One report of an ethylzinc m -terphenyl carboxylate, [Zn 2 (Ar Mes CO 2 ) 2 (Et) 2 ] ( 13 ), 11 is particularly interesting because it features two trigonal zinc centers (Ar Mes = 2,6-bis(mesityl)phenyl). The structure of 1 differs from that of 13 in that the latter has an eight-membered ring in a boat conformation (Figure 1), trigonal-planar zinc, and a Zn···Zn distance of 3.58 Å.…”

“…The 1 H NMR spectrum of 13 in C 6 D 6 supports the persistence of this structure in solution. 11 A summary of the carboxylate to ethyl ratios of the simple ethylzinc carboxylates is presented in Table S2 (Supporting Information). …”