Rare earths, scandium, yttrium, and the fifteen lanthanoids from lanthanum to lutetium, are classified as critical metals because of their ubiquity in daily life. They present magnets cars, especially electric cars; green electricity generating systems computers; steel manufacturing; glass light emission materials for safety lighting lasers; exhaust catalysts supports; artificial rubber production; agriculture animal husbandry; health cancer diagnosis treatment; a variety electronic products...

Merging two evolving areas in synthesis, namely cooperative bimetallics and N-heterocyclic carbenes (NHCs), this study reports the isolation of first intermediates alkali-metal-mediated zincation (AMMZn) a free NHC Zn–NHC complex using sodium zincate [(TMEDA)NaZn(TMP)(tBu)2] (1) as metallating reagent. The structural authentication (THF)3Na[:C{[N(2,6-iPr2C6H3)]2CHCZn(tBu2)}] (2) [Na(THF)6]+[tBu2Zn:C{[N(2,6-iPr2C6H3)]2CHCZn(tBu2)}]− (4), resulting from reactions 1 with unsaturated IPr (IPr =...

A series of triphenyl Sb(v) and Bi(v) α-hydroxy carboxylato complexes the general formula [MPh3(O2CROH)2] [MPh3(O2CRO)] have been successfully synthesised characterised, subsequently assayed for their comparative activity towards Leishmania parasites human fibroblast cells. Four are novel; [SbPh3Gly], [BiPh3(GlyH)2], [SbPh3(R-ManH)2] [SbPh3(S-ManH)2], structurally characterised through X-ray diffraction. These were combined in study with known complexes; ([SbPh3(R-Man)], [SbPh3(S-Man)],...

A series of organometallic bismuth(<sc>v</sc>) dicarboxylates, [BiPh₃(O₂CR′)₂], were synthesised and evaluated for their anti-leishmanial activity. The complexes are effective against parasite promastigotes (0.6–2.5 μM), but prone to slow reductive decomposition.

Meta–meta metalation: Remarkably, toluene can be directly dimanganated or dimagnesiated at the 3,5-positions using bimetallic bases with active Me3SiCH2 ligands (see scheme, blue). In contrast, n-butyl lead to 2,5-metalation (red). tmp=2,2,6,6-tetramethylpiperidide. Organolithium reagents have long enjoyed iconic status amongst synthetic chemists, in part because of their unrivaled ability affect directed metalation (lithiation, lithium–hydrogen exchange) reactions on arenes, heteroarenes,...

Abstract Extending the recently introduced concept of “alkali‐metal‐mediated manganation” to functionalised arenes, heteroleptic sodium manganate reagent [(tmeda)Na(tmp)(R)Mn(tmp)] ( 1 ; TMEDA= N , ′, ′‐tetramethylethylenediamine, TMP=2,2,6,6‐tetramethylpiperidide, R=CH 2 SiMe 3 ) has been treated with anisole or ‐diisopropylbenzamide in a 1:1 stoichiometry hexane. These reactions afforded crystalline products [(tmeda)Na(tmp)( o ‐C 6 H 4 OMe)Mn(tmp)] and [(tmeda)Na(tmp){ ‐{C(O)N( i Pr) C...

Performed with a desire to advance knowledge of the structures and mechanisms governing alkali-metal-mediated zincation, this study monitors reaction between TMP-dialkylzincate reagent [(TMEDA)Na(TMP)((t)Bu)Zn((t)Bu)] 1 trifluoromethyl benzene C(6)H(5)CF(3) 2. A complicated mixture products is observed at room temperature. X-ray crystallography has identified two these as ortho- meta-regioisomers heterotrianionic [(TMEDA)Na(TMP)(C(6)H(4)-CF(3))Zn((t)Bu)], 3-ortho 3-meta, respectively....

Comparing the reactivity of related lithium zincates [(THF)LiZn(TMP)(t)Bu(2)] (1) and [(PMDETA)LiZn(t)Bu(3)] (2) towards pyrazine discloses two new bimetallic approaches for selective 2,5-dideprotonation room temperature C-H alkylation this sensitive heterocycle.

Nine different β-thioxoketones of general formula R1C(O)CH2C(S)R2 (R1 = C6H5, R2 C6H5L1; R1 p-CF3C6H4L2; p-MeOC6H4, C6H5L3; p-CF3C6H4L4; C5H4N, C6H5L5; p-IC6H4, C6H5L6; p-IC6H4L7; C10H7L8 and CH3, C6H5L9) their tris-substituted bismuth(III) complexes having the [Bi{R1C(O)CHC(S)R2}3] were synthesised fully characterised. The solid state structure [Bi{C5H4NC(O)CHC(S)C6H5}3] B5 was determined by crystallography revealed that three β-thioxoketonato ligands are bound to centre in a bidentate...

A series of tris-tolylbismuth(<sc>v</sc>) dicarboxylates, [Bi(Tol)₃(O₂CR)₂], were synthesised, characterised and evaluated against<italic>Leishmania major</italic>parasites demonstrating good selectivity towards promastigotes but with more moderate success against amastigotes.

Abstract Homo‐ and heteroleptic bismuth thiolato complexes have been synthesised characterised from biologically relevant tetrazole‐, imidazole‐, thiadiazole‐ thiazole‐based heterocyclic thiones (thiols): 1‐methyl‐1 H ‐tetrazole‐5‐thiol (1‐MMTZ(H)); 4‐methyl‐4 ‐1,2,4‐triazole‐3‐thiol (4‐MTT(H)); ‐imidazole‐2‐thiol (2‐MMI(H)); 5‐methyl‐1,3,4‐thiadiazole‐2‐thiol (5‐MMTD(H)); 1,3,4‐thiadiazole‐2‐dithiol (2,5‐DMTD(H) 2 ); 4‐(4‐bromophenyl)thiazole‐2‐thiol (4‐BrMTD(H)). Reaction of BiPh 3 with...

Bismuth(<sc>iii</sc>) hydroxamate complexes of varying composition all show powerful bactericidal activity toward<italic>Helicobacter pylori</italic>.

Reaction of BiPh3 or Bi(O(t)Bu)3 with benzohydroxamic acid (H2-BHA) results in formation novel mono- and di-anionic hydroxamato complexes; [Bi2(BHA)3]∞ 1, [Bi(H-BHA)3] 2, [Bi(BHA)(H-BHA)] 3, all which display nM activity against Helicobacter pylori. Subsequent dissolution DMSO/toluene hydrolysis to the first structurally authenticated {Bi34} oxido-cluster [Bi34O22(BHA)22(H-BHA)14(DMSO)6] 4.

Full characterisation and catalytic potential of two NHC–Ag( i )amide complexes with the influence steric bulk NHC calculated via percent buried volume (% V Bur ), Solid-G ( G M ) AtomAccess .

With the aim of introducing diisopropylamide [NiPr(2)](-) ligand to alkali-metal-mediated manganation (AMMMn) chemistry, temperature-dependent reactions a 1:1:3 mixture butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, reaction affords surprising, ferrocene-free, hydrido product [Na(2)Mn(2) (mu-H)(2){N(iPr)(2)}(4)]2 toluene (1), first Mn inverse crown complex. Repeating...

Abstract Two new homo‐ and heteroleptic bismuth thiazole‐thiolato complexes derived from 4‐phenylthiazole‐2‐thiol MBT(H) have been synthesised structurally characterised, [BiPh(MBT) 2 ] [Bi(MBT) 3 . Syntheses were achieved using BiPh or Bi(O t Bu) in protolysis reactions with MBT(H), by salt metathesis BiCl BiPhCl the sodium thiolate, [NaMBT]. The obtained under both standard solvent‐free solvent‐mediated conditions, microwave irradiation. solid‐state structures of , determined...

Opening-up new synthetic applications of β-diketiminate stabilised magnesium complexes, this case study compares the ability alkyl [{Ar*NC(Me)CHC(Me)NAr*}Mg(Bu)(THF)] (1) and amido reagent [{Ar*NC(Me)CHC(Me)NAr*}Mg(TMP)] (2) (Ar* = 2,6-i-Pr2-C6H3) to promote direct Mg–H exchange towards series 1,3-benzoazoles: benzoxazole (boz), benzothiazole (btz) N-methyl benzimidazole (bImMe). Both reagents deprotonate boz at room temperature yield [{Ar*NC(Me)CHC(Me)NAr*}Mg{O(o-C6H4)NC}(THF)] (3) via C–O...

Five mixed thiolatobismuth(III) complexes [BiPh(5‐MMTD) 2 {4‐MMT(H)}] ( 1 ), [Bi(1‐MMTZ) {(PYM)(PYM(H)) }] [Bi(MBT) (5‐MMTD)] 3 [Bi(4‐BrMTD) {2‐MMI(H)}] 4 ) and {1‐MMTZ(H)}(2‐MMI){2‐MMI(H) 5 were synthesised from imidazole‐, thiazole‐, thiadiazole‐, triazole‐, tetrazole‐ pyrimidine‐based heterocyclic thiones. Four of these – synthesized BiPh , while complex was obtained Bi[4‐(MeO)Ph] . Complexes structurally characterised by XRD. Evaluation the antibacterial properties against Mycobacterium...

Alkali-metal-mediated manganation (AMMMn) reactions of the synergic base sodium monoalkyl-bisamidomanganate [(tmeda)Na(tmp)(CH(2)SiMe(3))Mn(tmp)] (1) with naphthalene, 1-methoxynaphthalene, or 2-methoxynaphthalene are reported. These novel direct [Mn(II)] produced crystalline ortho-manganated naphthyl products [(tmeda)Na(tmp)(2-C(10)H(7))Mn(tmp)] (3), [(tmeda)Na(tmp){2-(1-MeOC(10)H(6))}Mn(CH(2)SiMe(3))] (4), and [(tmeda)Na(tmp){3-(2-MeOC(10)H(6))}Mn(tmp)] (5) in reasonable to good isolated...

Ligand domin(o)ated: In contrast to the straightforward deprotonation of benzothiazole using Grignard reagents, treatment with 1 leads a novel type activation. The initial magnesiation initiates an unstoppable domino reaction CC coupling, ring opening, nucleophilic addition, and give 2. THF=tetrahydrofuran. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by...