Structures of a Clathrate Hydrate Former, Inhibitor, and Synergist in Water.

SANS studies are reported for aqueous THF at the 1:17 clathrate hydrate-forming composition and on aqueous solutions of the synergist 2-butoxyethanol. Addition of the clathrate hydrate inhibitor polyvinylcaprolactam and a dimeric model compound, 1,3-bis(caprolactamyl)butane, show that the inhibitors do not significantly affect the solution structures of these two important species in clathrate hydrate formation and inhibition. The SANS studies show that 1,3-bis(caprolactamyl)butane is a good model for polyvinylcaprolactam, and both the polymer and model compound exhibit hydrogen bonding interactions with water but do not interact significantly with 2-butoxyethanol in aqueous solution.

Modulating the hydration behaviour of calcium chloride by lactam complexation.

Complexation of calcium chloride with bis(lactam) ligand L1 allows the formation of both an unstable anhydrous complex, an aqua complex {[Ca2(µ-L1)2(H2O)9]Cl4]}n (1) and a related hydrate incorporating additional lattice water of crystallization {[Ca(µ-L1)(H2O)5]Cl2·H2O}n (2). Related mono(lactam) L2 does not form aqua complexes but the anhydrous complex {[CaCl2(µ-L2)2]}n (3), is highly deliquescent. An unusual ethanol solvate is also reported {[CaCl2(L2)(EtOH)]}n (4).

Highly interlocked anion-bridged supramolecular networks from interrupted imidazole-urea gels.

An imidazole urea displays switchable hydrogelation behaviour that is turned off by metal ion coordination to give anion-bound coordination complex arrays.

N-alkyl pyrrolidone ether podands as versatile alkali metal ion chelants.

This work explores the coordination chemistry of a bis(pyrrolidone) ether ligand. Pyrrolidones are commercially important functional groups because of the high polarity and hence high hydrophilicity and surface affinity. An array of alkali metal ion complexes of a podand bearing two pendant pyrrolidone functionalities, namely 1-{2-[2-(2-oxo-pyrrolid-1-yl)-ethoxy]-ethyl}-pyrrolid-2-one (1) are reported. Reaction of this ligand with sodium hexafluorophosphate gives two discrete species of formulae [Na(1)2]PF6 (3) and [Na3(H2O)2(µ-1)2](PF6)3 (4), and a coordination polymer {[Na3(µ3-1)3(µ2-1)](PF6)3}n (5). The same reaction in methanol gives a 1 : 1 complex, namely [Na2(µ-1)2(MeOH)2](PF6)2 (6). Use of tetraphenyl borate as a less coordinating counter ion gives [Na2(1)2(H2O)4](BPh4)2 (7) and [Na2(1)4](BPh4)2 (8). Two potassium complexes have also been isolated, a monomer [K(1)2]PF6 (9) and a cyclic tetramer [K4(µ4-H2O)2(µ-1)4](PF6)4 (10). The structures illustrate the highly polar nature of the amide carbonyl moiety within bis(pyrrolidone) ethers with longer interactions to the ether oxygen atom. The zinc complex is also reported and {[ZnCl2(µ-1)]}n (11) exhibits bonding only to the carbonyl moieties. The ether oxygen atom is not necessary for Na(+) complexation as exemplified by the structure of the sodium complex of the analogue 1,3-bis(pyrrolid-2-on-1-yl)butane (2). Reaction of compound 1 with lithium salts results in isolation of the protonated ligand.

The chemistry of low dosage clathrate hydrate inhibitors.

This review aims to introduce the chemistry of low dosage inhibitors of clathrate hydrate formation within the context of their role in the oil and gas industry. The review covers both kinetic hydrate inhibitors and anti-agglomerants from the point of view of structure-function relationships, focussing on recent refinements in mechanistic understanding and chemical design, and the consequently evolving and increasingly fine-tuned properties of these fascinating compounds.