studies of reversible solid-gas reactions of ethylene responsive silver pyrazolates.

Solid-gas reactions and powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF)Pz]Ag} and {[4-Br-3,5-(CF)Pz]Ag} supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF)Pz]Ag} under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above.

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO) } ] (M=Cu, Ag, Au).

Syntheses of the copper and gold complexes [Cu{Fe(CO) } ][SbF ] and [Au{Fe(CO) } ][HOB{3,5-(CF ) C H } ] containing the homoleptic carbonyl cations [M{Fe(CO) } ] (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu Fe, Ag Fe and Au Fe complexes [Cu{Fe(CO) } ][SbF ], [Ag{Fe(CO) } ][SbF ] and [Au{Fe(CO) } ][HOB{3,5-(CF ) C H } ] are also given. The silver and gold cations [M{Fe(CO) } ] (M=Ag, Au) possess a nearly linear Fe-M-Fe' moiety but the Fe-Cu-Fe' in [Cu{Fe(CO) } ][SbF ] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF ] anion.

Isolable 1-Butene Copper(I) Complexes and 1-Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates.

Non-porous small molecule adsorbents such as {[3,5-(CF ) Pz]Cu} (where Pz=pyrazolate) are an emerging class of materials that display attractive features for ethene-ethane separation. This work examines the chemistry of fluorinated copper(I) pyrazolates {[3,5-(CF ) Pz]Cu} and {[4-Br-3,5-(CF ) Pz]Cu} with much larger 1-butene in both solution and solid state, and reports the isolation of rare 1-butene complexes of copper(I), {[3,5-(CF ) Pz]Cu(H C=CHC H )} and {[4-Br-3,5-(CF ) Pz]Cu(H C=CHC H )} and their structural, spectroscopic, and computational data. The copper-butene adduct formation in solution involves olefin-induced structural transformation of trinuclear copper(I) pyrazolates to dinuclear mixed-ligand systems.

Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non-porous Copper(I) Complexes.

Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people.

An experimental and computational NMR study of organometallic nine-membered rings: Trinuclear silver(I) complexes of pyrazolate ligands.

This work reports the calculation of the nuclear magnetic resonance (NMR) chemical shifts of eight trinuclear Ag(I) complexes of pyrazolate ligands using the relativistic program ZORA. The data from the literature concern exclusively H, C, and F nuclei. For this reason, one of the complexes that is derived from 3,5-bis-trifluoromethyl-1H-pyrazole has been studied anew, and the N and Ag chemical shifts determined for the first time in solution.

Brightly phosphorescent tetranuclear copper(i) pyrazolates.

Described herein is the synthesis and photophysics of two tetranuclear copper complexes, {[3,5-(Pri)2,4-(Br)Pz]Cu}4 and {[3-(CF3),5-(But)Pz]Cu}4 tailor-designed by manipulating the pyrazolyl ring substituents. Unlike their trinuclear analogues, the luminescence of the tetranuclear species is molecular (not supramolecular) in nature with extremely high solid-state quantum yields of ∼80% at room temperature.

Acetylene and terminal alkyne complexes of copper(i) supported by fluorinated pyrazolates: syntheses, structures, and transformations.

Trinuclear {μ-[3,5-(CF)Pz]Cu} reacts with acetylene to produce the 2 : 1 copper(i) acetylene complex, Cu(μ-[3,5-(CF)Pz])(μ-HC[triple bond, length as m-dash]CH). Related Cu(μ-[4-Br-3,5-(CF)Pz])(μ-HC[triple bond, length as m-dash]CH) and Cu(μ-[4-Cl-3,5-(CF)Pz])(μ-HC[triple bond, length as m-dash]CH) have also been isolated using the corresponding copper(i) pyrazolate and acetylene. The 1 : 1 adducts Cu(μ-[3,5-(CF)Pz])(HC[triple bond, length as m-dash]CH) and Cu(μ-[4-Br-3,5-(CF)Pz])(HC[triple bond, length as m-dash]CH) are significantly less stable to the acetylene loss and can be observed in solution at low temperatures under excess acetylene.

Carbonyl complexes of copper(i) stabilized by bridging fluorinated pyrazolates and halide ions.

Syntheses of neutral and anionic, di- and tetra-nuclear copper carbon monoxide complexes using binary copper(i) pyrazolate precursors are reported. The reaction of {[3,5-(CF3)2Pz]Cu}3 (2), {[4-Cl-3,5-(CF3)2Pz]Cu}3 (3) or {[3,4,5-(CF3)3Pz]Cu}3 (4) with CO in CH2Cl2 led to copper carbonyl complexes. They however, lose CO quite easily if not kept under a CO atmosphere.

Low Heat of Adsorption of Ethylene Achieved by Major Solid-State Structural Rearrangement of a Discrete Copper(I) Complex.

The trinuclear copper(I) pyrazolate complex [Cu ] rearranges to the dinuclear analogue [Cu ⋅(C H ) ] when exposed to ethylene gas. Remarkably, the [Cu ]↔[Cu ⋅(C H ) ] rearrangement occurs reversibly in the solid state. Furthermore, this transformation emulates solution chemistry.

Mesoporous magnetic secondary nanostructures as versatile adsorbent for efficient scavenging of heavy metals.

Porous magnetic secondary nanostructures exhibit high surface area because of the presence of plentiful interparticle spaces or pores. Mesoporous Fe3O4 secondary nanostructures (MFSNs) have been studied here as versatile adsorbent for heavy metal scavenging. The porosity combined with magnetic functionality of the secondary nanostructures has facilitated efficient heavy metal (As, Cu and Cd) remediation from water solution within a short period of contact time.