Six- and five-coordinate Fe(II) complexes with the pincer ligand 2,6-bis(imidazolylidene)pyridine (C−N−C), [(C−N−C)Fe(MeCN)3][BPh4]2 [(C−N−C)FeBr2], respectively, were synthesized. Substitution of tmeda in [FeCl2(tmeda)]2 by C−N−C gave six-coordinate {[Fe(C−N−C)(C−N−C*)][FeCl4]}, which one ligands is bound to metal via 2- 5-imidazole carbons.

Reduction of the uranium(III) metallocene [(η5 -C5 i Pr5 )2 UI] (1) with potassium graphite produces "second-generation" uranocene U] (2), which contains uranium in formal divalent oxidation state. The geometry 2 is that a perfectly linear bis(cyclopentadienyl) sandwich complex, ground-state valence electron configuration uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f3 6d1 . Appreciable covalent contributions metal-ligand bonds were determined from...

Despite the unique position of gold catalysis in contemporary organic synthesis, this area research is notorious for requiring activators and/or additives that enable by generating cationic forms catalysts. Cycloisomerization reactions occupy a significant portion gold-catalyzed reaction space, while they represent diverse family are frequently utilized synthesis. Herein, hexafluoroisopropanol (HFIP) shown to be uniquely simple tool cycloisomerizations, rendering use external obsolete and...

A base-catalyzed protocol is reported for the construction of 1,3-thiazolidine-2-thione scaffolds bearing quaternary carbon centers from disulfide and α-tertiary propargylamines. The reaction proceeds using low catalyst loading, under ambient temperatures, in absence solvent. Various propargylamines have been employed, affording a series previously unreported thiazolidine-2-thione compounds avoiding purification via column chromatography certain cases. We also describe one-pot strategy...

The (diphenylphosphino)alkyl-functionalized nucleophilic heterocyclic carbene (NHC) complexes of palladium LPdX2 (L = (3-R1)[1-Ph2P(CH2)2]-imidazol-2-ylidene; R1 2,6-Pri2C6H3, 2,4,6-Me3C6H2; X CH3 (3a,b), Br (4a,b)) have been synthesized by the reaction in situ generated functionalized NHC ligand La or Lb with Pd(tmed)(CH3)2 and Pd(COD)Br2, respectively, structurally characterized. Interaction 3a H(Et2O){B[3,5-(CF3)2C6H2]4} pyridine (CF3)2CHOH CH2Cl2 gave monocationic...

Square planar neutral dimethyl and cationic allyl complexes of palladium with the electronically nonsymmetric diphenylphosphinomethyl- pyridyl-N-heterocyclic carbene ligands have been synthesized characterized. The products from protonation 1 equiv acid at low temperatures are monomethyl cations, exact nature which is dependent on type ligand; in pyridine−carbene Pd−Me bond cleaved trans to carbene, while for phosphino−carbene it phosphine. Density functional calculations suggest that these...

The addition of H(2) across a transition metal-borane bond is reported for the first time providing mechanism recharging borane functional groups to borohydride.

The selectivity of the mixed-sandwich U(III) complexes type [U(η-C8H6{SiiR3-1,4}2)(η-CpR′)] (R = Me, iPr; R′ Me4H, Me5, Me4iPr, Me4SiMe3, Me4Et) toward reductive coupling CO to form uranium-bound oxocarbons has been explored. In this context, new [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4TMS)], [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4iPr)], [U(η-C8H6{SiiPr3-1,4}2)(η-CpMe4Et)], [U(η-C8H6{SiMe3-1,4}2)(η-Cp*)], and [U(η-C8H6{SiMe3-1,4}2)(η-CpMe4TMS)] have prepared structurally characterized. reactivity is...

The uranium complexes [U(η⁸-C₈H₆(1,4-SiMe₃)₂)(η⁵-Cp^Me4R)] can be tuned to selectively reduce CO₂, giving U(<sc>iv</sc>) incorporating bridging oxo, carbonate, or oxalate groups.

The synthesis and molecular structures of a U(v) neutral terminal oxo complex sodium uranium nitride contact ion pair are described. the former is achieved by use t BuNCO as mild oxygen transfer reagent, whilst that latter via reduction NaN3. Both mono-uranium complexes stabilised presence bulky silyl substituents on ligand framework facilitate 2e- oxidation single U(iii) centre. In contrast, when steric hindrance around metal centre reduced less groups, products di-uranium, U(iv) bridging...

The first authenticated example of migration a methyl group from palladium(II) to coordinated N-heterocyclic carbene is described.

A family of benzotriazole based coordination compounds, obtained in two steps and good yields from commercially available materials, formulated as [CuII(L1)2(MeCN)2]·2ClO4·MeCN (1), [CuII(L1)(NO3)2]·MeCN (2), [ZnII(L1)2(H2O)2]·2ClO4·2MeCN (3), [CuII(L1)2Cl2]2 (4), [CuII5(L1)2Cl10] (5), [CuII2(L1)4Br2]·4MeCN·CuII2Br6 (6), [CuII(L1)2(MeCN)2]·2BF4 (7), [CuII(L1)2(CF3SO3)2] (8), [ZnII(L1)2(MeCN)2]·2CF3SO3 (9), [CuII2(L2)4(H2O)2]·4CF3SO3·4Me2CO (10), [CuII2(L3)4(CF3SO3)2]·2CF3SO3·Me2CO (11), are...

A new boron-based flexible scorpionate ligand based upon 7-azaindole, Li[Ph(H)B(azaindolyl)2] (Li[PhBai]), has been prepared. This ligand, together with the previously reported K[HB(azaindolyl)3] (K[Tai]), have used to prepare a range of monovalent group 9 transition-metal complexes. The complexes [M(COD){κ3N,N,H-Ph(H)B(azaindolyl)2}] (where M = rhodium, iridium and COD 1,5-cyclooctadiene) [Rh(NBD){κ3N,N,H-HB(R)(azaindolyl)2}] NBD 2,5-norbornadiene R Ph, azaindolyl) Structural...

The reaction of Ir(COD)(Tai) [where Tai = {HB(7-azaindoyl)3}−] with carbon monoxide results, via a sequence hydride migration and insertion steps, in the formation first complexes to contain metal-to-boron dative interaction supported by 7-azaindole units.

The synthesis and characterization of a homologous series T-shaped {MNO}

The synthesis of thiazolines, thiazolidines, and thiazolidinones has been extensively studied, due to their biological activity related neurodegenerative diseases, such as Parkinson's Alzheimer's, well antiparasitic antihypertensive properties. closely thiazolidin-2-imines have studied less, efficient strategies for synthesizing them, mainly based on the reaction propargylamines with isothiocyanates, explored less. use one-pot approaches, providing modular, straightforward, sustainable...

A study on the Mizoroki-Heck coupling of selected aryl bromides with acrylates catalysed by a series Pd complexes bidentate pyridyl-, picolyl-, diphenylphosphinoethyl- and diphenylphosphinomethyl-functionalised N-heterocyclic carbene (NHC) is reported. The observed activity dependent type solvent base used nature "classical" donors mixed-donor ligand its bite angle. mechanistic model presented for pyridine-functionalised NHC based an in situ EXAFS under dilute catalyst conditions (2 mM Pd)....

Rhodium and iridium complexes of flexible scorpionate ligands based on azaindole were synthesised in good yields. The characterised solution the solid state. Structural characterisation revealed a B–H–metal interaction, which is retained solution. Given greater flexibility ligand potential cooperative effect boron, tested for their activity transfer hydrogenation ketones.

The first structurally characterised zerovalent platinum complex to contain a tridentate pincer-type coordination mode (kappa(3)-SBS) is presented, raising further questions concerning the geometries and trans influence of Z-type ligands.

A ferrocene containing o-aminoanilide, N1-(2-aminophenyl)-N8-ferrocenyloctanediamide (2b, Pojamide) displayed nanomolar potency vs HDAC3. In comparison to RGFP966, a potent and selective HDAC3 inhibitor, Pojamide superior activity in HCT116 colorectal cancer cell invasion assays; however, TCH106 romidepsin, HDAC1 inhibitors, outperformed cellular proliferation colony formation assays. Together, these data suggest that HDAC1,3 inhibition is desirable achieve maximum anticancer benefits....

The reaction of the uranium(III) complex [U(η8-Pn††)(η5-Cp*)] (1) (Pn†† = C8H4(1,4-SiiPr3)2, Cp* C5Me5) with ethene at atmospheric pressure produces ethene-bridged diuranium [{(η8-Pn††)(η5-Cp*)U}2(μ-η2:η2-C2H4)] (2). A computational analysis 2 revealed that coordination to uranium reduces carbon–carbon bond order from a value consistent single bond, concomitant change in formal oxidation state +3 1 +4 2. Furthermore, uranium–ethene bonding is δ type, dominant contribution being f–d hybrid...

The 1 : reactions of uranium(iv) tetrakis(borohydride) with the sodium and potassium salts cyclobutadienyl anion [C4(SiMe3)4]2- (Cb'''') produce half-sandwich complexes [Na(12-crown-4)2][U(η4-Cb'''')(BH4)3] [U(η4-Cb'''')(μ-BH4)3{K(THF)2}]2. In 2 reaction U(BH4)4 Na2Cb'''', formation [U(η4-Cb'''')(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(BH4))]- reveals that a Cb'''' ligand undergoes an intramolecular deprotonation, resulting in allyl/tuck-in bonding mode. A computational study uranium-Cb'''' has...

The chemical investigation of the organic extract red alga Laurencia majuscula collected from Hurghada reef in Red Sea resulted isolation five C15 acetogenins, including four tricyclic ones maneonene type (1-4) and a 5-membered one (5), 15 sesquiterpenes, seven lauranes (6-12), cuparane (13), seco-laurane (14), snyderane (15), two chamigranes (16, 17), rearranged (18, 19) aristolane (20), as well diterpene (21) chlorinated fatty acid derivative (22). Among them, compounds 1-3, 5, 7, 8, 10,...