Fluorspar to fluorochemicals upon low-temperature activation in water.

The dangerous chemical hydrogen fluoride sits at the apex of the fluorochemical industry, but the substantial hazards linked to its production under harsh conditions (above 300 degrees Celsius) and transport are typically contracted to specialists. All fluorochemicals for applications, including refrigeration, electric transportation, agrochemicals and pharmaceuticals, are prepared from fluorspar (CaF) through a procedure that generates highly dangerous hydrogen fluoride. Here we report a mild method to obtain fluorochemicals directly from fluorspar, bypassing the necessity to manufacture hydrogen fluoride.

Surface forces and friction between Langmuir-Blodgett polymer layers in a nonpolar solvent.

Optimization of boundary lubrication by tuning the confined molecular structures formed by surface-active additives such as surfactants and polymers is of key importance to improving energy efficiency in mechanical processes. Here, using the surface forces apparatus (SFA), we have directly measured the normal and shear forces between surface layers of a functionalised olefin copolymer (FOCP) in n-dodecane, deposited onto mica using the Langmuir-Blodgett (LB) technique. The FOCP has an olefin backbone decorated with a statistical distribution of polar-aromatic groups, with a structure that we term as "centipede".

A Reflection on Sustainable Anode Materials for Electrochemical Chloride Oxidation.

Chloride oxidation is a key industrial electrochemical process in chlorine-based chemical production and water treatment. Over the past few decades, dimensionally stable anodes (DSAs) consisting of RuO - and IrO -based mixed-metal oxides have been successfully commercialized in the electrochemical chloride oxidation industry. For a sustainable supply of anode materials, considerable efforts both from the scientific and industrial aspects for developing earth-abundant-metal-based electrocatalysts have been made.

Magnesium, calcium and zinc [NN'] heteroscorpionate complexes.

A new family of sterically demanding N2N' heteroscorpionate pro-ligands (HC(tBu2pz)2SiMe2N(H)R (R = iPr, tBu, Ph, Xyl)) has been prepared via a straightforward modular synthetic route. An extensive study into the synthesis and characterisation of lithium, magnesium, calcium and zinc complexes supported by both 3,5-tBu and 3,5-Me substituted N2N' ligand families has been conducted. Attempted deprotonation of the pro-ligands with nBuLi afforded the corresponding lithium salts Li{HC(tBu2pz)2SiMe2NR} (R = iPr (1), tBu (2), Ph (3) and Xyl (4)) but air- and thermal-sensitivity limited the yields of these potentially useful precursors; only the sterically encumbered ligand system allowed clean reactivity.

Electronic Delocalization in Two and Three Dimensions: Differential Aggregation in Indium "Metalloid" Clusters.

Reduction of indium boryl precursors to give two- and three-dimensional M-M bonded networks is influenced by the choice of supporting ligand. While the unprecedented nanoscale cluster [In (boryl) ] (with an In @In @In (boryl) concentric structure), can be isolated from the potassium reduction of a bis(boryl)indium(III) chloride precursor, analogous reduction of the corresponding (benzamidinate)In Br(boryl) system gives a near-planar (and weakly aromatic) tetranuclear [In (boryl) ] system.

Enabling and Probing Oxidative Addition and Reductive Elimination at a Group 14 Metal Center: Cleavage and Functionalization of E-H Bonds by a Bis(boryl)stannylene.

By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H2 to a single site Sn(II) system has been achieved for the first time, generating (boryl)2SnH2. Similar chemistry can also be achieved for protic and hydridic E-H bonds (N-H/O-H, Si-H/B-H, respectively). In the case of ammonia (and water, albeit more slowly), E-H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-)borylated product.

Oxidative bond formation and reductive bond cleavage at main group metal centers: reactivity of five-valence-electron MX₂ radicals.

Monomeric five-valence-electron bis(boryl) complexes of gallium, indium, and thallium undergo oxidative M-C bond formation with 2,3-dimethylbutadiene, in a manner consistent with both the redox properties expected for M(II) species and with metal-centered radical character. The weaker nature of the M-C bond for the heavier two elements leads to the observation of reversibility in M-C bond formation (for indium) and to the isolation of products resulting from subsequent B-C reductive elimination (for both indium and thallium).

Stable GaX2, InX2 and TlX2 radicals.

The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized.

Potassium, zinc, and magnesium complexes of a bulky OOO-tridentate bis(phenolate) ligand: synthesis, structures, and studies of cyclic ester polymerisation.

Reaction of the OOO-coordinating tridentate bis(phenolate) protio-ligand 2,2'-{oxybis(methylene)}bis{4,6-di(1-methyl-1-phenylethyl)phenol} (L(O3)-H2), with 1 equiv. of KN(SiMe3)2 in toluene or THF yielded [K(L(O3)-H)] (1) or [K(L(O3)-H)(THF)] (2), respectively. Single-crystal X-ray diffraction studies of 1 and 2 revealed mononuclear structures with the phenyl rings of the bulky ligand displaying stabilising π-interactions to the potassium centre.

A generic one-pot route to acyclic two-coordinate silylenes from silicon(IV) precursors: synthesis and structural characterization of a silylsilylene.

Si in sight: a one-pot, single-step synthesis of an acyclic silylsilylene, Si{Si(SiMe(3))(3)}{N(SiMe(3))Dipp} (Dipp=2,6-iPr(2)C(6)H(3)), from a silicon(IV) starting material is reported, together with evidence for a mechanism involving alkali metal silylenoid intermediates.

A stable two-coordinate acyclic silylene.

Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)(2) substituent (Dipp = 2,6-(i)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C-H bonds, consistent with a low singlet-triplet gap (103.

Site selectivity and reversibility in the reactions of titanium hydrazides with Si-H, Si-X, C-X and H+ reagents: Ti=N(α) 1,2-silane addition, Nβ alkylation, Nα protonation and σ-bond metathesis.

We report a combined experimental and computational comparative study of the reactions of the homologous titanium dialkyl- and diphenylhydrazido and imido compounds Cp*Ti{MeC(N(i)Pr)(2)}(NNR(2)) (R = Me (1) or Ph (2)) and Cp*Ti{MeC(N(i)Pr)(2)}(NTol) (3) with silanes, halosilanes, alkyl halides and [Et(3)NH][BPh(4)]. Compound 1 underwent reversible Si-H 1,2-addition to Ti=N(α) with RSiH(3) (experimental ΔH ca. -17 kcal mol(-1)), and irreversible addition with PhSiH(2)X (X = Cl, Br).

Titanium tert-butoxyimido compounds.

The synthesis and molecular and electronic structures of the first tert-butoxyimido complexes of titanium (TiNO(t)Bu functional group) are reported, featuring a variety of mono- or poly-dentate, neutral or anionic N-donor ligands. Reaction of Ti(NMe(2))(2)Cl(2) with (t)BuONH(2) gave good yields of Ti(NO(t)Bu)Cl(2)(NHMe(2))(2) (1). Compound 1 serves as an excellent entry point into new tert-butoxyimido complexes by reaction with a variety of fac-N(3) donor ligands, namely, Me(3)[9]aneN(3) (trimethyl-1,4,7-triazacyclononane), HC(Me(2)pz)(3) (tris(3,5-dimethylpyrazolyl)methane), or Me(3)[6]aneN(3) (trimethyl-1,3,5-triazacyclohexane) to give Ti(NO(t)Bu)(Me(3)[9]aneN(3))Cl(2) (2), Ti(NO(t)Bu){HC(Me(2)pz)(3)}Cl(2) (3), or Ti(NO(t)Bu)(Me(3)[6]aneN(3))Cl(2) (4) in good yield.

Titanium alkoxyimido (Ti=N-OR) complexes: reductive N-O bond cleavage at the boundary between hydrazide and peroxide ligands.

The first Group 4 alkoxyimido compounds are reported. The Ti=N-O(t)Bu group in Ti(N(2)N(Me))(NO(t)Bu)(py) undergoes facile 2-electron N-O bond cleavage with PhCCMe as the reductant to form a 1,2-diamidoalkene group via two highly selective N-C bond forming events.

Group 3 and lanthanide boryl compounds: syntheses, structures, and bonding analyses of Sc-B, Y-B, and Lu-B σ-coordinated NHC analogues.

Reaction of [Ln(CH(2)SiMe(3))(2)(THF)(n)][BPh(4)] (Ln = Sc, Y, Lu ; n = 3, 4) with Li{B(NArCH)(2)}(THF)(2) (Ar = 2,6-C(6)H(3)(i)Pr(2)) formed the first group 3 and lanthanide boryl compounds, Sc{B(NArCH)(2)}(CH(2)SiMe(3))(2)(THF) and Ln{B(NArCH)(2)}(CH(2)SiMe(3))(2)(THF)(2) (Ln = Y, Lu), which contain two-center, two-electron Ln-B σ bonds. All of these systems were crystallographically characterized. Density functional theory analysis of the Ln-B bonding found it to be predominantly ionic, with covalent character in the σ-bonding Ln-B HOMO.

Reaction site diversity in the reactions of titanium hydrazides with organic nitriles, isonitriles and isocyanates: Ti=N(α) cycloaddition, Ti=N(α) insertion and N(α) -N(β) bond cleavage.

We report a range of new transformations of the diamide-amine supported Ti=NNPh(2) functional group with a variety of unsaturated substrates, along with DFT studies of the key mechanisms. Reaction of [Ti(N(2) N(py) )(NNPh(2) )(py)] (4, N(2) N(py) =(2-NC(5) H(4) )CMe(CH(2) NSiMe(3) )(2) ; py=pyridine) with MeCN gave the dimeric species [Ti(2) (N(2) N(py) )(2) {μ-NC(Me)(NNPh(2) )}(2) ] through a [2+2] cycloaddition process. Reaction of 4 or [Ti(N(2) N(Me) )(NNPh(2) )(py)] (5, N(2) N(Me) =MeN(CH(2) CH(2) NSiMe(3) )(2) ) with fluorinated benzonitriles gave the terminal hydrazonamide complexes [Ti(N(2) N(R) ){NC(Ar F x)NNPh(2) }(py)] (R=py or Me; Ar F x=2,6-C(6) H(3) F(2) or C(6) F(5) ).

M=N(alpha) cycloaddition and N(alpha)-N(beta) insertion in the reactions of titanium hydrazido compounds with alkynes: a combined experimental and computational study.

A combined experimental and DFT study of the reactions of diamide-amine supported titanium hydrazides with alkynes is presented. Reaction of Ti(N2N(py))(NNPh2)(py) (1, N2N(py) = (2-NC5H4)CMe(CH2NSiMe3)2) with terminal and internal aryl alkynes ArCCR (Ar = Ph or substituted phenyl, R = Me or H) at room temperature gave the fully authenticated azatitanacyclobutenes Ti(N2N(py)){N(NPh2)C(R)CAr} via ArCCR [2 + 2] cycloaddition to the Ti=N(alpha) bond of the hydrazide ligand. In contrast, reaction of 1 with PhCCMe at 60 degrees C, or of Ti(N2NMe)(NNPh2)(py) (11, N2NMe = MeN(CH2CH2NSiMe3)2) with RCCMe (R = Me, Ph or substituted phenyl) at room temperature or below, gave vinyl imido compounds of the type Ti(N2N(R')){NC(R)C(Me)NPh2}(py), in which RCCMe had undergone net insertion into the N(alpha)-N(beta) bond.

Dicationic and zwitterionic catalysts for the amine-initiated, immortal ring-opening polymerisation of rac-lactide: facile synthesis of amine-terminated, highly heterotactic PLA.

Dicationic, zwitterionic and "conventional" yttrium compounds act as catalysts for the primary or secondary amine-initiated immortal ROP of rac-lactide; amine-terminated, highly heterotactic poly(rac-lactides) with narrow polydispersities and well-controlled molecular weights are prepared in this manner.

Sulfonamide-supported group 4 catalysts for the ring-opening polymerization of epsilon-caprolactone and rac-lactide.

Reaction of RCH(2)N(CH(2)CH(2)NHSO(2)Tol)(2) (R = 2-NC(5)H(4) (8, H(2)L(py)) or MeOCH(2) (9, H(2)L(OMe))) with Ti(NMe(2))(4) at room temperature afforded Ti(L(py))(NMe(2))(2) (10) or Ti(L(OMe))(NMe(2))(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding reactions with Ti(O(i)Pr)(4) or Zr(O(i)Pr)(4) x HO(i)Pr required more forcing conditions to form the homologous bis(isopropoxide) analogues, M(L(R))(O(i)Pr)(2) (M = Ti, R = py (12) or OMe (14); M = Zr, R = py (13) or OMe (15)). Reaction of Ti(NMe(2))(2)(O(i)Pr)(2) with H(2)L(R) formed 12 or 14 under milder conditions.

Sodium, magnesium and zinc complexes of mono(phenolate) heteroscorpionate ligands.

The reaction of bis(3,5-dimethylpyrazolyl)methylphenol N(2)O(Ar)H (1) with NaH in THF formed dimeric [Na(kappa(2)-N(2)O(Ar))(THF)](2) (2), which contains a kappa(2)(N,O)-bound bidentate N(2)O(Ar) ligand. The reaction of 1 with Mg(n)Bu(2) gave the four-coordinate monomeric butyl compound Mg(N(2)O(Ar))(n)Bu (3), whereas with (n)BuMgCl, a mixture of products was formed, including the six-coordinate homoleptic species Mg(N(2)O(Ar))(2) (4). The reaction of [Na(kappa(2)-N(2)O(Ar))(THF)](2) with (n)BuMgCl also gave 3, as did the redistribution reaction of Mg(n)Bu(2) with 4.

Synthesis, structures and reactivity of group 4 hydrazido complexes supported by calix[4]arene ligands.

Reaction of TiCl(2)(Me(2)Calix) with 2 equiv of LiNHNRR' afforded the corresponding terminal hydrazido(2-) complexes Ti(NNRR')(Me(2)Calix) (R = Ph, R' = Ph (1) or Me; R = R' = Me (3)) which were all structurally characterized. The X-ray structure of Ph(2)NNH(2) is reported for comparison. Compound 1 was also prepared from Na(2)[Me(2)Calix] and Ti(NNPh(2))Cl(2)(py)(3).

Cycloaddition reactions of transition metal hydrazides with alkynes and heteroalkynes: coupling of Ti=NNPh2 with PhCCMe, PhCCH, MeCN and tBuCP.

The first structurally authenticated [2+2] cycloaddition products of any transition metal hydrazide complexes are reported; cycloaddition products of transition metal hydrazides with alkynes and heteroalkynes have been obtained for the first time; these are the first structurally authenticated cycloaddition products for any transition metal M=NNR(2) functional group.

Zwitterionic bis(phenolate)amine lanthanide complexes for the ring-opening polymerisation of cyclic esters.

The reaction of Sm{N(SiMe3)2}3 with the bis(phenol)amines H2O2N(R) (H2O2N(R) = RCH2CH2N(2-HO-3,5-C6H2(t)Bu2)2; R = OMe, NMe2 or Me) gave exclusively zwitterions Sm(O2N(R))(HO2N(R)). For R = OMe or NMe2 these were efficient catalysts for the ring-opening polymerisation of epsilon-caprolactone and D,L-lactide with a tendency to form cyclic esters; in contrast, no polymerisation was observed for R = Me.