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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". The effect of lateral confinement, characterised by the surface pressure, Π dep , at the air-water interface at which the LB films are transferred, was examined. Normal force profiles revealed that the thickness of the LB films increased significantly with Π dep , with the film thickness (t > 20 nm) inferring a multi-layered film structure, consistent with the interfacial characterisation results from synchrotron X-ray reflectivity (XRR) measurements. The coefficient of friction, µ, between the LB films spanned two orders of magnitude from superlubricity (µ ∼ 0.002) to much higher friction (µ > 0.1) depending nonlinearly on Π dep , with the lowest friction observed at the intermediate Π dep . Molecular arrangement upon LB compression leads to the multilayer film with a structure akin to an interfacial gel, with transient crosslinking facilitated by the intra- and inter-molecular interactions between the functional groups. We attribute the differences in frictional behaviour to the different prevalence of the FOCP functional groups at the lubricating interface, which depends sensitively on the degree of compression at the air-water interface prior to the LB deposition. The LB films remain intact after repeated compression (up to pressures of 10 MPa) and shear cycles, indicating strong surface anchorage and structural robustness as a load-bearing and shear-mediating boundary layer. These unprecedented results from the friction measurements between LB films of a statistical copolymer in oil point towards new strategies for tailoring macromolecular architecture for mediating efficient energy dissipation in oil-based tribological applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

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 2 - and IrO 2 -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. This review first describes the history of commercial DSA fabrication and strategies to improve their efficiency and stability. Important features related to the electrocatalytic performance for chloride oxidation and reaction mechanism are then summarized. From the perspective of sustainability, recent progress in the design and fabrication of noble-metal-free anode materials, as well as methods for evaluating the industrialization of novel electrocatalysts, are highlighted. Finally, future directions for developing highly efficient and stable electrocatalysts for industrial chloride oxidation are proposed., (© 2023 Wiley-VCH GmbH.)

To predict the behavior of gas-cleaning filters during real-world operation, it is essential to understand their response to ambient conditions. The temporary presence of water droplets in gas-cleaning filtration systems due to fog, spray rain, or condensation, as examples of irregular events, has an impact on the filters' operating performance, especially when soluble particles are present. In this work, surface filters were loaded with mixtures of water-soluble salt particles and insoluble glass spheres. These were, subsequently, exposed to water mist and dried by a particle-free gas stream. A novel approach to analyze the drainage of solution on filters with soluble filter cakes is presented, which allows the detection of solubles on the clean gas side of the filter. As a result, this work, for the first time, presents a sighting of the penetration of soluble filter cake material through gas-cleaning filters. Furthermore, filter performance, in terms of differential pressure and fractional separation efficiency, was determined and a characteristic differential pressure evolution for hydrophilic filters during exposure to water mist was also identified. The fractional separation efficiency of gas-cleaning filters decreases due to exposure to water mist. The findings are supported by scanning electron microscopy (SEM) images, energy-dispersive X-ray (EDX), and X-ray microtomography (µ-CT analysis) images.

Objective: To assess whether positive flow cytometry quantification of fetal red blood cells is associated with adverse maternal and neonatal outcomes in cases of mild trauma during pregnancy., Study Design: A retrospective database study was conducted at a single tertiary center between 2013 and 2019. All pregnant women with viable gestation involved in trauma who underwent flow cytometry quantification of fetal red blood cells were included in the study. Flow cytometry was considered positive (≥0.03/≥30 ml). Composite adverse maternal and neonatal outcome was defined as one or more of the following: intrauterine fetal death, placental abruption, pre-term birth <37 weeks of gestation, immediate premature rupture of the membranes, and immediate delivery following trauma. Univariate analysis was performed followed by multivariate logistic regression analysis controlling for potential confounders, to assess the role of flow cytometry in predicting adverse maternal and neonatal outcome. Adjusted odds ratios (aORs) and 95% confidence intervals (CIs) were calculated., Results: During the study period 1023 women met inclusion and exclusion criteria. The mechanisms of injury were motor vehicle accident in 387 women (38%), falls in 367 (36%), direct abdominal injury in 353 (35%) and in 14 women (1%) other mechanism of injury. Flow cytometry was considered positive (≥0.03/≥30 ml) in 119 women (11.6%) with median result of 0.03 [0.03-0.04], and negative in 904 women (88.4%) ((≤0.03/≤30 ml) with median result of 0.01 [0.01-0.02]. Composite adverse outcome occurred in 8% of the women involved in trauma during pregnancy, with no difference between the groups with vs. without positive flow cytometry (4.2% vs. 8.5%; p = 0.1). Positive flow cytometry was not associated with any adverse maternal or neonatal outcome. This was confirmed on multivariate analysis controlling for potential confounders., Conclusion: Flow cytometry result is not related to adverse maternal and fetal/neonatal outcome of women involved in minor trauma during pregnancy. We suggest that flow cytometry should not be routinely assessed in pregnant women involved in minor trauma., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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. Magnesium methyl complexes Mg{HC(tBu2pz)2SiMe2NR}Me (R = iPr (5) and R = Ph (6)) were prepared using an excess of the Grignard reagent MeMgCl. Magnesium butyl complexes were synthesised in good yields using the dialkyl precursor MgnBu2 to afford Mg{HC(R'2pz)2SiMe2NR}nBu (R' = Me; R = iPr (7), tBu (8), Ad (9), Ph (10). R' = tBu; R = iPr (11), Ph (12)). Protonolylsis reactions were used to synthesise magnesium and calcium amide complexes Mg{HC(R'2pz)2SiMe2NR}{N(SiHMe2)2} (R' = Me; R = iPr (13), tBu (14), Ph (15). R' = tBu; R = Ph (16)) or Mg{HC(R'2pz)2SiMe2NR}{N(SiMe3)2} (R' = Me; R = iPr (17), tBu (18), Ph (19). R' = tBu; R = Ph (20)), and Ca{HC(R'2pz)2SiMe2NR}{N(SiMe2)2} (L) (R' = Me; L = thf; R = iPr (21), tBu (22), Ph (23). R' = tBu; L = none; R = Ph (24). Zinc methyl complexes Zn{HC(R'2pz)2SiMe2NR}Me (R' = Me; R = iPr (25), tBu (26), Ph (27). R' = tBu; R = Ph (28)) were prepared by reaction of the N2N' heteroscorpionate pro-ligands with ZnMe2. In preliminary studies, magnesium amide complexes 16 and 20 were evaluated as initiators for the ring-opening polymerisation (ROP) of ε-caprolactone (ε-CL) and rac-lactide (rac-LA). Although the overall polymerisation control was poor, 16 and 20 were found to be active initiators.

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 68 (boryl) 12 ] - (with an In 12 @In 44 @In 12 (boryl) 12 concentric structure), can be isolated from the potassium reduction of a bis(boryl)indium(III) chloride precursor, analogous reduction of the corresponding (benzamidinate)In III Br(boryl) system gives a near-planar (and weakly aromatic) tetranuclear [In 4 (boryl) 4 ] 2- system., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: The number of terror attack incidents is on the increase worldwide. The knife is one of the weapons most commonly used among terrorists. Appropriate preparation in trauma units for coping with the increasing numbers of terrorist-inflicted stabbings is different from the preparation suitable for civilian stabbings. Therapeutic and logistic guidelines need to be adjusted to accommodate those differences., Objectives: Characterize the unique injuries related to terrorist stabbing, and suggest preparedness actions., Methods: Retrospective data on all terrorist-inflicted stabbing incidents between September 2015 and May 2016 were retrieved from the database of the national Israeli emergency medical services and from the Israeli Defense Forces Medical Corps records., Results: There were a total of 414 civilian victims (34 fatalities) of terror incidents. Of these, 161 involved stabbings during 106 separate incidents. There was more than 1 stab wound per patient in approximately 60% of cases, and more than 1 victim in approximately 40% of cases. Unlike civilian stabbings, terrorist stabbings were characterized by more commonly occurring to the upper part of the body, being executed by large knives with high force, and involving multiple and more severe injuries., Conclusion: There is a clear distinction between the characteristics of wounds resulting from civilian stabbings and those incurred by acts of terror. Terrorists intend to injure as many random victims as possible, and trauma units need to be prepared to cope with the simultaneous admission of multiple patients with penetrating and often life-threatening knife wounds., (Copyright © 2017 Elsevier Inc. All rights reserved.)

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. Thus, in stoichiometric fashion, redox-based bond cleavage/formation is demonstrated for a single main group metal center at room temperature. From a mechanistic viewpoint, a two-step coordination/proton transfer process for N-H activation is shown to be viable through the isolation of species of the types Sn(boryl)2·NH3 and [Sn(boryl)2(NH2)](-) and their onward conversion to the formal oxidative addition product Sn(boryl)2(H)(NH2).

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).

Synthetic routes to the first boryl complexes of cadmium and mercury are reported via transmetallation from boryllithium; the syntheses of related group 14 systems highlight the additional factors associated with extension to more redox-active post-transition elements.

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. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.

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. L(O3)-H2 also reacts with 1 equiv. of ZnEt2 or Mg(n)Bu2 to give [M2(L(O3))2] (M = Zn (3) or Mg (4)) in good yield. The molecular structures of complex 3 and 4 reveal dinuclear species in which the metal centres are tetra-coordinated to the three oxygen atoms of one L(O3) ligand, and to the bridging oxygen atom of one phenolate group of another. Complexes 1-4 are catalysts for ring-opening polymerisation of ε-caprolactone and L- and rac-lactide in the presence of benzyl alcohol (BnOH) and also other initiators to give the corresponding polyesters. Kinetic studies for the ROP of ε-caprolactone using 3 and BnOH gives an unusual rate expression R(p) = -d[CL]/dt = k(p)[BnOH]0[3]0(0.5) for which a tentative kinetic model is proposed.

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., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 (103.9 kJ mol(-1)), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems., (© 2012 American Chemical Society)

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). DFT found that the reaction products and certain intermediates were stabilised by β-NMe(2) coordination to titanium. The Ti-D bond in Cp*Ti{MeC(N(i)Pr)(2)}(D){N(NMe(2))SiD(2)Ph} underwent σ-bond metathesis with BuSiH(3) and H(2). Compound 1 reacted with RR'SiCl(2) at N(α) to transfer both Cl atoms to Ti; 2 underwent a similar reaction. Compound 3 did not react with RSiH(3) or alkyl halides but formed unstable Ti=N(α) 1,2-addition or N(α) protonation products with PhSiH(2)X or [Et(3)NH][BPh(4)]. Compound 1 underwent exclusive alkylation at N(β) with RCH(2)X (R = H, Me or Ph; X = Br or I) whereas protonation using [Et(3)NH][BPh(4)] occurred at N(α). DFT studies found that in all cases electrophile addition to N(α) (with or without NMe(2) chelation) was thermodynamically favoured compared to addition to N(β).

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. It was found that 4 could be converted into Ti(NO(t)Bu)Cl(2)(py)(3) (5) in very good yield by reaction with an excess of pyridine. Compound 5 is effective in a range of salt metathesis reactions with lithiated amide or pyrrolide ligands, and reacts with Li(2)N(2)N(py), Li(2)N(2)N(Me), LiN(pyr)N(Me(2)), or Li(2)N(2)(pyr)N(Me) to give Ti(N(2)N(py))(NO(t)Bu)(py) (6), Ti(N(2)N(Me))(NO(t)Bu)(py) (7), Ti(N(pyr)N(Me(2)))(NO(t)Bu)Cl(py)(2) (9), or Ti(N(2)(pyr)N(Me))(NO(t)Bu)(py)(2) (10) in moderate to good yields (N(2)N(py) = (2-NC(5)H(4))C(Me)(CH(2)NSiMe(3))(2); N(2)N(Me) = MeN(CH(2)CH(2)NSiMe(3))(2); N(pyr)N(Me(2)) = Me(2)NCH(2)(2-NC(4)H(3)); N(2)(pyr)N(Me) = MeN{CH(2)(2-NC(4)H(3))}(2)). Compounds 7, 9, and 10 reacted with 2,2'-bipyridyl by pyridine exchange reactions forming Ti(N(2)N(Me))(NO(t)Bu)(bipy) (8), Ti(N(pyr)N(Me(2)))(NO(t)Bu)Cl(bipy) (11), and Ti(N(2)(pyr)N(Me))(NO(t)Bu)(bipy) (12). Ten tert-butoxyimido compounds, namely, 1-6, 11, and 12, have been structurally characterized revealing approximately linear Ti-N-O(t)Bu linkages with Ti-N distances [range 1.686(2)-1.734(2) Å] that are generally intermediate between those in the homologous alkylimido and phenylimido analogues, and shorter than in the diphenylhydrazido counterparts. Density functional theory (DFT) studies on the model compounds Ti(NR)Cl(2)(NHMe(2))(2) (1&#95;R; R = OMe, Me, Ph, NMe(2)) confirmed this trend and found that the destabilizing effect of the -OMe oxygen 2p(π) lone pair on one of the Ti-N π-bonds in 1&#95;OMe is comparable to that of the occupied phenyl ring π orbitals in the phenylimido homologue 1&#95;Ph but much less than for the -NMe(2) nitrogen lone pair in 1&#95;NMe(2).

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., (© The Royal Society of Chemistry 2011)

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.

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) ). DFT studies showed that this proceeds through an overall [2+2] cycloaddition-reverse cycloaddition, resulting in net insertion of Ar F xCN into the Ti=N(α) bonds of the respective hydrazides. Reaction of 4 with a mixture of MeCN and PhCCMe gave the metallacycle [Ti(N(2) N(py) ){NC(Me)C(Ph)C(Me)NNPh(2) }] by sequential coupling of Ti=NNPh(2) with PhCCMe and then MeCN. A related product, [Ti(N(2) N(py) ){NC(Me)C(Ar(F) )C(H)NNPh(2) }], was formed by insertion of MeCN into the Ti-C bond of the isolated azatitanacyclobutene [Ti(N(2) N(py) ){N(NPh(2) )C(H)C(Ar(F) )}] (Ar(F) =3-C(6) H(4) F). Reaction of 4 with two equivalents of B(Ar F 5)(3) (Ar F 5=C(6) F(5) ) formed the zwitterionic borate [Ti(N(2) N(py) ){η(2) -N(NPh(2) )B(Ar F 5)(3) }] by electrophilic attack at N(α) . Compounds 4 and 5 reacted with tBuNC and/or XylNC (Xyl=2,6-C(6) H(3) Me(2) ) to give the N(α)-N(β) bond cleavage products, [Ti(N(2) N(R) )(NCNR')(NPh(2) )] (R=py or Me; R'=tBu or Xyl), containing metallated carbodiimide ligands. DFT studies of these reactions found an initial addition of RNC across Ti=N(α) followed by N(β) coordination, and finally complete N(α) transfer from the NNPh(2) to the RNC fragment. Reaction of 5 with Ar'NCE (E=O, S, Se; Ar'=2,6-C(6) H(3) iPr(2) ) gave the [2+2] cycloaddition products [Ti(N(2) N(Me) ){N(NPh(2) )C(NAr')O}(py)] and [Ti(N(2) N(Me) ){N(NPh(2) )C(NAr')E}] (E=S or Se), which did not undergo further transformation of the Ti-N-NPh(2) moiety., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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. These are the first examples of this type of reaction for any metal hydrazide. The reaction of 11 with PhCCMe had the activation parameters DeltaH(double dagger) = 18.8(4) kcal mol(-1), DeltaS(double dagger) = 1(1) cal mol(-1) K(-1) and DeltaG(298)(double dagger) = 18.5(7) kcal mol(-1). Mechanistic and DFT studies for 1 and 11 found that the N(alpha)-N(beta) insertion event is preceded by alkyne cycloaddition to Ti=N(alpha), and that N(alpha)-N(beta) bond "insertion" is really an intramolecular N(alpha) atom migration process within the azatitanacyclobutenes following intramolecular chelation of NPh2 of the hydrazide ligand. Electron-withdrawing aryl groups on ArCCMe stabilize the azatitanacyclobutenes and also promote a specific regiochemistry (ArC carbon bound to Ti). This in turn defines the regiochemistry of the overall N(alpha)-N(beta) insertion reaction (ArC carbon bound to N(alpha)). In contrast, electron-releasing aryl groups promote the final N(alpha) migration stage of the mechanism, and a Hammett analysis of the rates of insertion of (4-C6H4X)CCMe into the N(alpha)-N(beta) bond of 11 found a reaction constant, rho, of -0.74(5), consistent with NPA charge changes of ArC along the DFT reaction coordinate.

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.

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. The X-ray structures of 10-15 have been determined revealing C(s) symmetric, 6-coordinate complexes except for 13 which is 7-coordinate with one kappa(2)(N,O) bound sulfonamide donor. Compounds 10-15 are all catalysts for the ring-opening polymerization (ROP) of epsilon-caprolactone, with the isopropoxide compounds being the fastest and best controlled, especially in the case of zirconium. In addition, Zr(L(OMe))(O(i)Pr) (2) (15) was an efficient catalyst for the well-controlled ROP of rac-lactide both in toluene at 100 degrees C and in the melt at 130 degrees C, giving atactic poly(rac-lactide). The polymerization rates and control achieved for 13 and 15 are comparable to those of the well-established bis(phenolate)amine-supported Group 4 systems reported recently.

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. The reaction of 1 with Mg{N(SiRMe(2))(2)}(2) afforded the four-coordinate amide derivatives Mg(N(2)O(Ar)){N(SiRMe(2))(2)} (R = Me (6) or H (7)), together with 4. The reactions of 1 with ZnMe(2) or Zn{N(SiMe(3))(2)}(2) gave the monomeric compounds Zn(N(2)O(Ar))Me (8) and Zn(N(2)O(Ar)){N(SiMe(3))(2)} (9), respectively. The reaction 9 of with HCl formed Zn(N(2)O(Ar))Cl (11), and subsequent addition of LiN(SiHMe(2))(2) to 11 led to Zn(N(2)O(Ar)){N(SiHMe(2))(2)} (12). The reaction of 1 with either Zn{N(SiMe(3))(2)}(2) or 9 gave Zn(N(2)O(Ar))(2). The compounds 2, 3, 4, 6, 8, 9 and 11 were crystallographically characterized. Compound was very active for the ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) but the process was very poorly controlled as judged by the M(n) and polydispersity index of the polymer. Compounds 3, 8, 9 and 12 gave poor conversions to poly(epsilon-CL) over extended periods. N(2)O(Ar)H = 2,4-di-tert-butyl-6-(bis(3,5-dimethylpyrazolyl)methyl)phenol.

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). Reaction of ZrCl(2)(Me(2)Calix) with 2 equiv of LiNHNR(2) afforded only the bis(hydrazido(1-)) complexes Zr(NHNR(2))(2)(Me(2)Calix) (R = Ph or Me). Treatment of Ti(NNMe(2))(Me(2)Calix) (3) with MeI gave the zwitterionic hydrazidium species Ti(NNMe(3))(MeCalix) (6) via a net isomerization reaction which was found to be catalytic in MeI. The corresponding reaction of 3 with CD(3)I gave Ti(NNMe(2)CD(3))(MeCalix) (6-d(3)) with concomitant elimination of MeI. Reaction of 3 with 1 equiv of MeOTf gave [Ti(NNMe(3))(Me(2)Calix)][OTf] (7-OTf) which in turn reacted with (n)Bu(4)NI to form 6 and MeI. Addition of PhCHO to 3 gave the mu-oxo dimer [Ti(mu-O)(Me(2)Calix)](2) and benzaldehyde-dimethylhydrazone. Reaction of either 3 or 6 with (t)BuNCO gave the zwitterionic species Ti{(t)BuNC(NNMe(3))O}(MeCalix) (10) which has been crystallographically characterized. Compound 10 is the formal product of insertion of an isocyanate into the Ti=N(alpha) bond of a titanium hydrazide or hydrazidium species (Me(2)Calix or MeCalix = dianion or trianion of the di- or monomethyl ether of p-tert-butyl calix[4]arene, respectively).

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.

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.

Two broadly applicable strategies for extending the available ligand platforms of the virtually unexplored terminal Ti=N-NR2 functional group are described, along with the highly selective room temperature insertion of alkynes into the N-N bond of Ti{MeN(CH2CH2NSiMe3)2}(NNPh2)(py) and the catalytic cis-diamination of PhC[triple bond]CMe by diphenylhydrazine.