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Multinuclear Zinc Pentafluorobenzene Carboxylates: Synthesis, Characterization, and Hydrogen Storage Capability

DOI: 10.1021/om100703c DOI Help

Authors: Carl Redshaw (University of East Anglia) , Surajit Jana (University of East Anglia) , Congxiao Shang (University of East Anglia) , Mark Elsegood (Loughborough University) , Xuesong Lu (University College London) , Zheng Xiao Guo (University College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Organometallics , VOL 29 (22)

State: Published (Approved)
Published: October 2010

Abstract: Zinc carboxylates are of great interest owing to their role in biochemical systems, catalysis, and materials chemistry. For instance, alkoxyzinc carboxylates are attracting attention owing to their importance as highly active catalysts for the polymerization or copolymerization of a wide range of organic monomers.(1) Recently, they have been utilized as structural units/nodes in metal−organic polymers (MOPs) and frameworks (MOFs); such systems have shown promising adsorption behavior with a variety of small molecules including methane, nitrogen, and hydrogen.(2-4) A variety of related alkylzinc complexes containing carboxylate-based ligands have also been prepared, most notably alkyl(R)zinc carbamato complexes, [RZn(O2CNR′2)], and alkylzinc carboxylates for which the carboxylate group contains a second coordinating functionality, [RZn(O2CR′X)] (X = OH, NH2, SH).(5-8) The alkylzinc carbamato species, prepared by CO2 insertion into Zn−N bonds, form discrete tetramers of the type [MeZn(μ3-O2CNR′2)]4, which become dimers of the form [MeZn(μ2-O2CNR′2)(py)]2 on the addition of pyridine (py) (NR′2 = N(iPr)2, N(iBu)2, and piperidinyl). Dickie et al. reported the reaction of diethylzinc with 2,6-bis(2,4,6-trimethylphenyl)benzoic acid, in which the bulky carboxylate groups enforce a low coordination number at the metal centers, leading to dimeric [EtZn(μ2-O2CR)]2.(9) Mitzel et al. reported the pentanuclear zinc hydroxylamide cluster [(iPrZn)4Zn(ONMe2)6],(10) comprising an octahedral-based structure with all six O,N ligands O-bound to the central Zn2+; similar findings were observed in the cadmium hydroxylamide cluster [(MeCd)4Cd(ONEt2)6].(11) Lewinski et al. reported the alkylzinc carboxylate [EtZn(O2CPh)]6, a precursor to zinc oxocarboxylates [Zn4O(O2CPh)6] and the sulfidocarboxylates [Zn3(μ3-S)(OOCPh)(thf)]2.(12) The double tetrahedral core complex [Zn7O2(O2CMe)10(1-Meim)2] (1-Meim = 1-methylimidazole) has been isolated from the reaction of Zn(OAc)2┬ĚH2O and 1-methylimidazole in refluxing acetonitrile.(13) More recently, Shaffer and Williams et al. reported the pentanuclear alkylzinc carboxylate [Zn5(O2CCH3)6(Et)4], formed by the reaction of diethylzinc with zinc acetate.(14)

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 25/10/2010 08:21

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