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The illicit manufacture of drugs in the 21st century presents a danger to first responders, bystanders and the environment, making its detection important. Electronic noses based on metal oxide semiconducting (MOS) sensors present a potential technology to create devices for such purposes. An array of four thick film MOS gas sensors was fabricated, based on zinc oxide inks. Production took place using a commercially available screen printer, a 3 x 3 mm alumina substrate containing interdigitated electrodes and a platinum heater track. ZnO inks were modified using zeolite β, zeolite Y and mordenite admixtures. The sensors were exposed to four gases commonly found in the clandestine laboratory environment; these were nitrogen dioxide, ethanol, acetone and ammonia. Zeolite modification was found to increase the sensitivity of the sensor, compared to unmodified ZnO sensors, all of which showed strong responses to low ppm concentrations of acetone, ammonia and ethanol and to ppb concentrations of nitrogen dioxide. Machine learning techniques were incorporated to test the selectivity of the sensors. A high level of accuracy was achieved in determining the class of gas observed. [ABSTRACT FROM AUTHOR]

The overall performance of lithium batteries remains unmatched to this date. Decades of optimisation have resulted in long-lasting batteries with high energy density suitable for mobile applications. However, the electrolytes used at present suffer from low lithium transference numbers, which induces concentration polarisation and reduces efficiency of charging and discharging. Here we show how targeted modifications can be used to systematically evolve anion structural motifs which can yield electrolytes with high transference numbers. Using a multidisciplinary combination of theoretical and experimental approaches, we screened a large number of anions. Thus, we identified anions which reach lithium transference numbers around 0.9, surpassing conventional electrolytes. Specifically, we find that nitrile groups have a coordination tendency similar to SO 2 and are capable of inducing the formation of Li + rich clusters. In the bigger picture, we identified a balanced anion/solvent coordination tendency as one of the key design parameters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Air and moisture stable diaryl dithiocarbamate salts, Ar 2 NCS 2 Li, result from addition of CS 2 to Ar 2 NLi, the latter being formed upon deprotonation of diarylamines by n BuLi. Oxidation with K 3 [Fe(CN) 6 ] affords the analogous thiuram disulfides, (Ar 2 NCS 2 ) 2 , two examples of which (Ar = p -C 6 H 4 X; X = Me, OMe) have been crystallographically characterised. The interconversion of dithiocarbamate and thiuram disulfides has also been probed electrochemically and compared with that established for the widely-utilised diethyl system. While oxidation reactions are generally clean and high yielding, for Ph(2-naphthyl)NCS 2 Li an ortho -cyclisation product, 3-phenylnaphtho[2,1- d ]thiazole-2(3 H )-thione, is also formed, resulting from a competitive intramolecular free-radical cyclisation. To demonstrate the coordinating ability of diaryl dithiocarbamates, a small series of Co(III) complexes have been prepared, with two examples, [Co{S 2 CN( p -tolyl) 2 } 3 ] and [Co{S 2 CNPh( m -tolyl)} 3 ] being crystallographically characterised. Solvothermal decomposition of [Co{S 2 CN( p -tolyl) 2 } 3 ] in oleylamine generates phase pure CoS 2 nanospheres in an unexpected phase-selective manner.

Ionic liquids are becoming increasingly popular for practical applications such as biomass processing and lithium-ion batteries. However, identifying ionic liquids with optimal properties for specific applications by trial and error is extremely inefficient since there are a vast number of potential candidate ions. Here we combine experimental and computational techniques to determine how the interplay of fluorination, flexibility and mass affects the transport properties of ionic liquids with the popular imide anion. We observe that fluorination and flexibility have a large impact on properties such as viscosity, whereas the influence of mass is negligible. Using targeted modifications, we show that conformational flexibility provides a significant contribution to the success of fluorination as a design element. Contrary to conventional wisdom, fluorination by itself is thus not a guarantor for beneficial properties such as low viscosity., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

[FeFe]-Ase biomimics containing a redox-active ferrocenyl diphosphine have been prepared and their ability to reduce protons and oxidise H 2 studied, including 1,1'-bis(diphenylphosphino)ferrocene (dppf) complexes Fe 2 (CO) 4 (μ-dppf)(μ-S(CH 2 ) n S) ( n = 2, edt; n = 3, pdt) and Fe 2 (CO) 4 (μ-dppf)(μ-SAr) 2 (Ar = Ph, p -tolyl, p -C 6 H 4 NH 2 ), together with the more electron-rich 1,1'-bis(dicyclohexylphosphino)ferrocene (dcpf) complex Fe 2 (CO) 4 (μ-dcpf)(μ-pdt). Crystallographic characterisation of four of these show similar overall structures, the diphosphine spanning an elongated Fe-Fe bond ( ca. 2.6 Å), lying trans to one sulfur and cis to the second. In solution the diphosphine is flexible, as shown by VT NMR studies, suggesting that Fe 2 ⋯Fe distances of ca. 4.5-4.7 Å in the solid state vary in solution. Cyclic voltammetry, IR spectroelectrochemistry and DFT calculations have been used to develop a detailed picture of electronic and structural changes occurring upon oxidation. In MeCN, Fe 2 (CO) 4 (μ-dppf)(μ-pdt) shows two chemically reversible one-electron oxidations occurring sequentially at Fe 2 and Fc sites respectively. For other dppf complexes, reversibility of the first oxidation is poor, consistent with an irreversible structural change upon removal of an electron from the Fe 2 centre. In CH 2 Cl 2 , Fe 2 (CO) 4 (μ-dcpf)(μ-pdt) shows a quasi-reversible first oxidation together with subsequent oxidations suggesting that the generated cation has some stability but slowly rearranges. Both pdt complexes readily protonate upon addition of HBF 4 ·Et 2 O to afford bridging-hydride cations, [Fe 2 (CO) 4 (μ-H)(μ-dcpf)(μ-pdt)] + , species which catalytically reduce protons to generate H 2 . In the presence of pyridine, [Fe 2 (CO) 4 (μ-dppf)(μ-pdt)] 2+ catalytically oxidises H 2 but none of the other complexes do this, probably resulting from the irreversible nature of their first oxidation. Mechanistic details of both proton reduction and H 2 oxidation have been studied by DFT allowing speculative reaction schemes to be developed.

In this work we investigate the structure-property relationships in a series of alkylimidazolium ionic liquids with almost identical molecular weight. Using a combination of theoretical calculations and experimental measurements, we have shown that re-arranging the alkyl side chain or adding functional groups results in quite distinct features in the resultant ILs. The synthesised ILs, although structurally very similar, cover a wide spectrum of properties ranging from highly fluid, glass forming liquids to high melting point crystalline salts. Theoretical ab initio calculations provide insight on minimum energy orientations for the cations, which then are compared to experimental X-ray crystallography measurements to extract information on hydrogen bonding and to verify our understanding of the studied structures. Molecular dynamics simulations of the simplest (core) ionic liquids are used in order to help us interpret our experimental results and understand better why methylation of C 2 position of the imidazolium ring results in ILs with such different properties compared to their non-methylated analogues.

The reaction between differently substituted borasiloxanes and 2,5-bis(3-pyridylethynyl)thiophene provided the first example of luminescent borasiloxane-based chiral helices held together by N-B bonds. The starting building blocks and the helices were fully characterized, and the nature of the N-B bond rationalized by means of theoretical calculations.

A tetracarboxylic acid with a methyl-substituted siloxane core (L-H 4 ) has been prepared and applied in the construction of water stable MOFs with low water affinity. L-H 4 itself crystallizes as an interpenetrated 3D hydrogen-bonded network. Reaction of L-H 4 with Zr IV /Hf IV gave IMP-32-Zr/Hf - both 3D MOFs of scu topology.

The behaviour of two molecular rotors, one charged - 3,3'-diethylthiacarbocyanine iodide (Cy3) and one neutral - 8-[4-decyloxyphenyl]-4,4-difluoro-4-bora-3 a ,4 a -diaza- s -indacene (BODIPY-C10), have been studied in various ionic liquids. The fluorescent decay lifetime has been used to elucidate the structure of the immediate region around the rotor. The neutral BODIPY-C10 was found to prefer the non-polar alkyl chain environment, leading to two trends in the lifetime of the dye: one when it was fully partitioned into the non-polar domain, and one when it also sampled polar moieties. The positively charged Cy3 dye showed a complex relationship between the bulk viscosity of the ionic liquid and lifetime of the molecular rotor. This was attributed to a combination of polarity related spectral changes, changes in anion cages around the dye, and temperature dependent fluorescent lifetimes alongside the dependence of the rotor upon the viscosity., (This journal is © The Royal Society of Chemistry 2020.)

The identification of specific design concepts for the in silico design of ionic liquids (ILs) has been accomplished using theoretical methods. Molecular building blocks, such as interchangeable functional groups, are used to design a priori new ILs which have subsequently been experimentally investigated. The conformational design concepts are developed by separately and systematically changing the central (imide), bridging (sulfonyl) and end (trifluoromethyl) group of the bis(trifluoromethanesulfonyl)imide [N(Tf) 2 ] - anion and examining the resultant potential energy surfaces. It is shown that these design concepts can be used to tune separately the minimum energy geometry, transition state barrier height and relative stability of different conformers. The insights obtained have been used to design two novel anions for ILs, trifluoroacetyl(methylsulfonyl)imide [N(Ms)(TFA)] - and acetyl(trifluoromethanesulfonyl)imide [N(Tf)(Ac)] - . The computationally predicted structures show excellent agreement with experimental structures obtained from X-ray crystallography. [C 4 C 1 im][N(Tf)(Ac)] and [C 4 C 1 im][N(Ms)(TFA)] ILs have been synthesised and ion diffusion coefficients examined using pulsed field gradient stimulated echo NMR spectroscopy. Significantly increased diffusion was observed for the more flexible [N(Tf)(Ac)] - compared with the more rigid [N(Ms)(TFA)] - analogue. Furthermore, a pronounced impact on the fluidity was observed. The viscosity of the IL with the rigid anion was found to be twice as high as the viscosity of the IL with the flexible anion. The design concepts presented in this work will enable researchers in academia and industry to tailor anions to provide ILs with specific desired properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This paper reports the synthesis of the novel single-source precursor, [{(MeInAs t Bu) 3 } 2 (Me 2 InAs( t Bu)H) 2 ] and the subsequent first report of aerosol-assisted chemical vapour deposition of InAs thin films. Owing to the use of the single-source precursor, highly crystalline and stoichiometric films were grown at a relatively low deposition temperature of 450 °C. Core level XPS depth profiling studies showed some partial oxidation of the film surface, however this was self-limiting and disappeared on etch profiles. Valence band XPS analysis matched well with the simulated density of state spectrum. Hall effect measurements performed on the films showed that the films were n-type with promising resistivity (3.6 × 10 -3 Ω cm) and carrier mobility (410 cm 2 V -1 s -1 ) values despite growth on amorphous glass substrates.

We present investigations into a variety of supporting electrolytes and supercritical fluids probing the phase and conductivity behaviour of these systems and show that they not only provide sufficient electrical conductivity for an electrodeposition bath, but match the requirements imposed by the different precursors and process parameters, e.g. increased temperature, for potential deposition experiments. The two supercritical fluids that have been explored in this study are difluoromethane (CH2F2) and 1,1-difluoroethane (CHF2CH3). For CH2F2, the phase behaviour and electrical conductivity of eight ionic compounds have been studied. Each compound consists of a cation and an anion from the selected candidates i.e. tetramethylammonium ([N(CH3)4](+)), tetrabutylammonium ([N((n)C4H9)4](+)), 1-ethyl-3-methylimidazolium ([EMIM](+)) and 1-butyl-3-methylimidazolium ([BMIM](+)) for cations, and tetrakis(perfluoro-tert-butoxy)aluminate ([Al(OC(CF3)3)4](-)), chloride (Cl(-)), trifluoromethyl sulfonimide ([NTf2](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) for anions. For CHF2CH3, [N((n)C4H9)4][BF4] and [N((n)C4H9)4][B{3,5-C6H3(CF3)2}4] have been investigated for comparison with the previously measured solubility and conductivity in CH2F2. We have found that [N((n)C4H9)4][Al(OC(CF3)3)4], [N((n)C4H9)4][FAP] and [N(CH3)4][FAP] have much higher molar conductivity in scCH2F2 at similar conditions than [N((n)C4H9)4][BF4], a widely used commercial electrolyte. Additionally, scCHF2CH3 shows potential for use as the solvent for supercritical fluid electrodeposition, especially at high temperatures since high density of this fluid can be achieved at lower operating pressures than similar fluids that can be used to produce electrochemical baths with comparable conductivity.

A new route to cationic complexes of Mg, Ca, Sr and Ba with 18-membered ring O4S2, O4Se2 and O2S4 donor macrocycles from metal acetonitrile complexes with weakly coordinating [BAr(F)](-) anions is described. The precursors used were [M(MeCN)x][BAr(F)]2 (M = Mg, x = 6; M = Ca, x = 8) and [M'(acacH)(MeCN)5][BAr(F)]2 (M' = Sr or Ba). Reaction of these with the heterocrowns, [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane), [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane) or [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane) in anhydrous CH2Cl2 solution gave [M(heterocrown)(MeCN)2][BAr(F)]2 for M = Mg, Ca or Sr, whilst the larger Ba forms [Ba(heterocrown)(acacH)(MeCN)][BAr(F)]2. The complexes have been characterised by microanalysis, IR, (1)H and (13)C{(1)H} NMR spectroscopy. X-ray crystal structures are reported for [Ca([18]aneO2S4)(MeCN)2][BAr(F)]2, [Ca([18]aneO4Se2)(MeCN)2][BAr(F)]2, [Sr([18]aneO4S2)(MeCN)2][BAr(F)]2, and [Sr([18]aneO4Se2)(MeCN)2][BAr(F)]2 which contain 8-coordinate metal centres with trans-nitrile ligands and κ(6)-heterocrowns, and for the 9-coordinate [Ba([18]aneO4Se2)(acacH)(MeCN)][BAr(F)]2. Adventitious hydrolysis of the magnesium complexes in solution results in six-coordinate complexes, [Mg(κ(3)-[18]aneO4Se2)(OH2)2(MeCN)][BAr(F)]2 and [Mg(κ(3)-[18]aneO4S2)(OH2)2(MeCN)][BAr(F)]2, whose structures were determined. X-ray crystal structures are also reported for [Mg(MeCN)6][BAr(F)]2, [M(MeCN)8][BAr(F)]2 (M = Ca, Sr) and [Ca(18-crown-6)(MeCN)2][BAr(F)]2.

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show κ(3)-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(iv) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BAr(F); [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BAr(F)], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BAr(F)], contain distorted octahedral cations, with facialκ(3)-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BAr(F)] and [SiBr3(pmdta)][BAr(F)] under similar conditions, containing mer-octahedral cations.

The complexes [M(L)][BAr(F)] (BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), L = [18]aneO4S2 (1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane): M = Li-Cs; L = [18]aneO2S4 (1,10-dioxa-4,7,13,16-tetrathiacyclooctadecane): M = Li, Na, K; L = [18]aneO4Se2 (1,4,10,13-tetraoxa-7,16-diselenacyclooctadecane): M = Na, K, as well as [Na(18-crown-6)][BAr(F)], are obtained in good yield as crystalline solids by reaction of M[BAr(F)] with the appropriate macrocycle in dry CH2Cl2. X-ray crystallographic analyses of [Li([18]aneO4S2)][BAr(F)] and [Li([18]aneO2S4)][BAr(F)] show discrete distorted octahedral cations with hexadentate coordination to the macrocycle. The heavier alkali metal complexes all contain hexadentate coordination of the heterocrown, supplemented by MF interactions via the anions, producing extended structures with higher coordination numbers; Na: CN = 7 or 8; K: CN = 8; Rb: CN = 9; Cs: CN = 8 or 10. Notably, all of the structures exhibit significant M-S/Se coordination. The crystal structures of the potassium and rubidium complexes show two distinct [M(heterocrown)](+) cations, one with MF interactions to two mutually cis [BAr(F)](-) anions, and the other with mutually trans [BAr(F)](-) anions, giving 1D chain polymers. Solution multinuclear ((1)H, (13)C, (7)Li, (23)Na, (133)Cs) NMR data show that the macrocyclic coordination is retained in CH2Cl2 solution.

The Group 1 complexes, [M(Me6[18]aneN6)][BAr(F)] (M = Li-Cs; Me6[18]aneN6 = 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; BAr(F) = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), are obtained in high yield by reaction of the macrocycle with M[BAr(F)] in anhydrous CH2Cl2 solution, and characterised spectroscopically ((1)H, (13)C{(1)H}, (7)Li, (23)Na, and (133)Cs NMR), by microanalysis and, for M = Li, K, and Rb, by single crystal X-ray analysis. The structures show N6-coordination to the metal ion; the small ionic radius for Li(+) leads to a puckered conformation. In contrast, the K(+) ion fits well into the N6 plane, with the [BAr(F)](-) anions above and below, leading to two K(+) species in the asymmetric unit (a hexagonal planar [K(Me6[18]aneN6)](+) cation and a '[K(Me6[18]aneN6)(κ(1)-BAr(F))2](-) anion', with long axial KF interactions). The Rb(+) ion sits above the N6 plane, with two long axial RbF interactions in one cation and two long, mutually cis RbF interactions in the other. The unusual sandwich cations, [M(Me3tacn)2](+) (M = Na, K; distorted octahedral, N6 donor set) and half-sandwich cations [Li(Me3tacn)(thf)](+) (distorted tetrahedron, N3O donor set), [Li(Me4cyclen)(OH2)](+), and [Na(Me4cyclen)(thf)](+) (both distorted square pyramids with N4O donor sets) were also prepared (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Density functional theory (DFT) calculations, using the BP86 and B3LYP functionals, show that the accessibility of the [M(Me3tacn)2](+) sandwich cations depends strongly on the M(+) ionic radius, such that it is sufficiently large to avoid steric clashing between the Me groups of the two rings, and small enough to avoid very acute N-M-N chelate angles. The calculations also show that coordination to the Group 1 cation involves significant donation of electron density from the p-orbitals on the N atoms of the macrocycle, rather than purely electrostatic interactions.

The new binary mixed-valence fluoride of germanium, Ge3F8, has been obtained by heating GeF4 with powdered Ge in an autoclave (390 K/4 bar/48 h). The structure contains pyramidal Ge(II)F3 and octahedral Ge(IV)F6 units, linked by fluoride bridges. The new compound is the missing member of the series (GeF2)n·GeF4 (n = 2, 4, or 6). Sublimation of (GeF2)n·GeF4in vacuo provides a convenient source of GeF2 in ca. 30% overall yield.

Highly unusual Na(+) complexes with neutral tri- and tetra-amines are isolable in good yield from the reaction of NaBAr(F) with the amine in organic media. Structural characterisation reveals primary Na-N bonding, including an unusual sandwich cation [Na(Me3tacn)2](+), derived from homoleptic N6-coordination via two Me3-tacn ligands, and the distorted 5-coordinate [Na(thf)(Me4cyclam)](+).

Reaction of SnF2 in MeOH with the appropriate neutral N- or O-donor ligands produces [SnF(2,2'-bipy)]2SnF6, [SnF(1,10-phen)]2SnF4 and [SnF2(L)] L = Me3PO, dmso or pyNO). The X-ray structures of [SnF(2,2'-bipy)]2SnF6, [SnF(1,10-phen)]2SnF4 and [SnF2(dmso)], reveal trigonal pyramidal Sn(II) cores with longer fluorine bridges completing distorted 5- or 6-coordination. Attempts to prepare SnF2 adducts with various phosphine or diphosphine ligands in MeCN failed, whilst in CH2Cl2 solution complex reactions involving the solvent occurred. The NHC, 1,3-(2,6-di-isopropylphenyl)imidazol-2-ylidene (IDiPP) and SnF2 produced the imidazolium salt, [IDiPPH]SnF3, the crystal structure of which revealed the first example of a discrete trifluorostannate(II) ion. In contrast, diphosphine complexes of tin(II) chloride formed readily, including [SnCl2{Me2P(CH2)2PMe2}], [SnCl2{o-C6H4(PMe2)2}], [SnCl2{o-C6H4(PPh2)2}] and [(SnCl2)2(μ-Ph2P(CH2)2PPh2)], which were characterised by X-ray crystallography. The structures of [SnCl2{Me2P(CH2)2PMe2}] and [SnCl2{o-C6H4(PMe2)2}] reveal chloride-bridged dimers, but [SnCl2{o-C6H4(PPh2)2}], although also dimeric, has very asymmetric diphosphine coordination best described as κ(1). The structures of [(SnCl2)2(μ-Ph2P(CH2)2PPh2)] and of [SnCl{o-C6H4(AsMe2)2}]SnCl3 reveal trigonal pyramidal cores, but with longer Sn···Cl bridges affording polymeric structures. The synthesis of [SnCl2(R3EO)2] (R = Ph, E = P or As; and R = Me, E = P) are also reported, along with the structure of [SnCl2(Me3PO)2], which contains distorted tetragonal pyramidal Sn(II) coordination. X-ray structures are also reported for [(PMe3)2CH2][SnCl3]2 and [Ph2P(H)(CH2)2P(H)Ph2][SnCl3]2, obtained as by-products from the attempts to synthesise phosphine complexes, as well as [(o-C6H4(PMe2)2CH2]I2. All complexes were characterised by microanalysis, IR and multinuclear NMR spectroscopy ((1)H, (19)F{(1)H}, (31)P{(1)H } and, where solubility allowed, (119)Sn). Comparisons are drawn with corresponding Sn(IV) and Ge(II) complexes.

[MF(4)(dmso)(2)] (M = Zr or Hf) and [MF(4)(dmf)(2)], prepared by dissolving MF(4)·nH(2)O in the appropriate solvent, have been used as synthons for a range of complexes of these otherwise intractable tetrafluorides. These reagents react with OPR(3) (R = Me or Ph) or OAsPh(3) (L) in anhydrous CH(2)Cl(2) to form six-coordinate [MF(4)L(2)] which exist as a mixture of cis (predominant form) and trans isomers in CH(2)Cl(2) solution but which crystallise as trans (OPPh(3), OAsPh(3)) or cis (OPMe(3)) forms. Cis-[ZrF(4)(OAsPh(3))(2)] crystals were obtained from MeCN. Cis-[MF(4)(pyNO)(2)] and eight-coordinate (distorted dodecahedral) [MF(4)(L-L)(2)] (L-L = 2,2'-bipy, or 1,10-phen), and [MF(4)(Me(4)-cyclam)] were also obtained. Attempts to prepare complexes with the N-heterocyclic carbene, 1,3-(2,6-di-isopropylphenyl)imidazol-2-ylidene (IDiPP) or alkyl diphosphines were unsuccessful. Crystal structures are reported for trans-[ZrF(4)(OPPh(3))(2)], cis- and trans-[ZrF(4)(OAsPh(3))(2)], cis-[HfF(4)(OPMe(3))(2)], [ZrF(4)(2,2'-bipy)(2)], cis-[HfF(4)(dmf)(2)], and geometric isomers (both pentagonal bipyramidal) of [(dmso)(2)F(3)M(μ-F)(2)MF(3)(dmso)(2)]. The failed attempts to make IDiPP adducts led to crystals of [IDiPPH](3)[M(3)F(15)] containing discrete anions based upon a triangle of M atoms with single F bridges. The results are compared with previous work on TiF(4) adducts and with complexes of MCl(4), and demonstrate that the MF(4) are very hard Lewis acids, with a marked preference for O- over N-donors.

Five titanium arsine compounds have been synthesised via the reaction of TiCl(4) with AsPh(3) (1 : 1 and 1 : 2 equivalents), or one equivalent of Ph(2)AsCH(2)AsPh(2), (t)BuAsH(2) and As(NMe(2))(3). In general, 1 : 1 and 1 : 2 adducts of the type [TiCl(4)(L)(n)] (n = 1, L = AsPh(3), Ph(2)AsCH(2)AsPh(2), and (t)BuAsH(2); n = 2, L = AsPh(3)), were isolated and characterised. However, the reaction of TiCl(4) with As(NMe(2))(3) resulted in a novel exchange between a Cl and an NMe(2) group, yielding the product [TiCl(3)(NMe(2))(mu-NMe(2))(2)AsCl]. The crystal structure of [TiCl(3)(NMe(2))(mu-NMe(2))(2)AsCl] has been determined and showed that the titanium and arsenic atoms are linked via two bridging NMe(2) groups. Additionally, crystal structures for the 1 : 1 and 1 : 2 adducts, [TiCl(4)(AsPh(3))] and [TiCl(4)(AsPh(3))(2)] have been obtained, with Ti-As bond lengths of 2.7465(13) and 2.7238(7) A observed respectively. The decomposition of the compounds has been investigated using thermogravimetric analysis, aerosol-assisted and low pressure chemical vapour deposition.

Reactions of Fe(C-N-C)(N2)2, 1a, or Fe(C-NMe-C)(N2)2, 1b, C-N-C = 2,6-bis(arylimidazol-2-ylidene)pyridine, C-NMe-C = 2,6-bis(arylimidazol-2-ylidene)-3,5-dimethylpyridine, aryl = 2,6-iPr2C6H3, with silanes are described. Complex 1a with excess SiPhH3 and complex 1b with excess Si(tol)H3, Ph = phenyl, C6H5, tol = 2-methylphenyl, gave the complexes [Fe(C-N-C)(SiH2Ph)2(2-H-SiH2Ph)], 2a, and [Fe(C-NMe-C)(SiH2tol)2(2-H-SiH2tol)], 2b, respectively. Complex 1b with excess SiPhH3 gave [Fe(C-NMe-C)(SiH2Ph)2(H)2], 3, which was formulated as a dihydride based on the relaxation time T1(min) in the 1H-NMR spectra. Reaction of 1a with SiPh2H2 gave complex [Fe(C-N-C)(SiHPh2)2(2-H2)], 4, while reaction with Si(mes)H3 gave complex [Fe(C-N-C)(SiH2mes)2(N2)], 5, mes = mesityl, 2,4,6-trimethylphenyl. The comparison of the reactivity with other pincer complexes of iron and the mechanism leading to 2a-5 are discussed.

The reaction of NiBr2(DME), DME = 1,2-dimethoxyethane, with the pincer pyridine dicarbene ligands (C-N-C) ( 2) and (C-NMe-C) ( 2Me), (C-N-C = 2,6-bis-[(DiPP)imidazol-2-ylidene]pyridine, C-NMe-C = 2,6-bis-[(DiPP)imidazol-2-ylidene]-3,5-dimethylpyridine, DiPP = 2,6-diisopropylphenyl) gave the square planar complexes [Ni(C-N(Me)-C)Br]Br, 3.( Br)- and 3Me.( Br)- respectively. Transmetallation from [(C-NMe-C)2Ag2](Ag6I8), 6Me.( Ag6 I8)2- to NiBr2(DME) gave [Ni(C-NMe-C)Br](AgI2), 3Me.( AgI2)-. Reaction of 3.( Br)- with KPF6 resulted only in exchange of the ionic bromide, however the reaction of 3.( Br)- with AgBF4 in MeCN or AgOTf in THF resulted in the exchange of both coordinated and ionic bromides, giving rise to the square planar 4.( BF4)-2 and octahedral 5, respectively. In contrast, the reaction of 3Me.( AgI2)-, with excess AgOTf resulted in an unusual reverse transmetallation leading to 6Me.( OTf)-. The substitution of tmeda in Ni(CH3)2(tmeda), tmeda = N,N,N,N-tetramethylethylenediamine, by 2 produced the complex 7, in which ring opening of the heterocyclic imidazole ring of one of the NHC functional groups has taken place.

A new method leading to Ni(NHC)2 (NHC = IMes, IPri, SIPr(i), SIBu(t)) complexes in moderate to good yields, involves the reaction of NHC (pre-formed or generated in situ) with Ni(CH3)2(tmed), tmed = N,N'-tetramethylethylenediamine; in one case, the intermediate Ni[I(Me2)Pr(i)]2(CH3)2, I(Me2)Pr(i) = N,N'-diisopropyl-4,5-dimethylimidazol-2-ylidene, has been isolated and structurally characterised.

Hyper-Rayleigh scattering is revealed as a very sensitive monitor of cluster formation in solution, and as a means of studying the mechanism of crystal nucleation in molecular species. Two compounds are selected with particularly high second harmonic generation (SHG) powers in the crystalline state and experimental conditions are defined allowing the measurement of the beta value for one of these as 18+/-1x10(-30) esu. It is found to agree with current theoretical prediction of 20x10(-30) esu. In the more powerful of these, two photon induced fluorescence is found to be partly responsible for the SHG. The solubilities of both compounds in methanol are measured and it is observed that these differ by a factor of ten. When the solution concentration is increased beyond 45% of the saturation value, the quadratic coefficient exhibits non-linear behaviour with respect to concentration. Additionally, the widths of the distributions of the HRS signals increase initially with concentration as expected, but, beyond 45% saturation concentrations, these narrow again. These phenomena are interpreted as indicators of cluster formation in these solutions well below saturation concentrations. A future experimental design is proposed in which the coherent component will yield information on the organisation of the molecules in such clusters.

The complexes [(C-N-C)MX(n)(thf)(m)] with the 'pincer' 2,6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C-N-C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C-N-C)(=O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl2 8. The complex trans-Ti(C-N-C)(=NBu(t))Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu(t))Cl2(py)3 by C-N-C.