The six-membered heavy atom heterocycles [Re2(CO)8(μ-SbPh2)(μ-H)]2, 5, and Pd[Re2(CO)8(μ-SbPh2)(μ-H)]2, 7, have been prepared by the palladium-catalyzed ring-opening cyclo-dimerization of three-membered heterocycle Re2(CO)8(μ-SbPh2)(μ-H), 3. palladium that lies in center 7 was removed to yield 5. removal found be partially reversible leading an unusual example host–guest behavior. A related dipalladium complex Pd2Re4(CO)16(μ4-SbPh)(μ3-SbPh2)(μ-Ph)(μ-H)2, 6, also formed these reactions with

The synthesis of a rare trivalent Th3+ complex, (C5Me5)2[iPrNC(Me)NiPr]Th, initiated density functional theory analysis on the electronic and molecular structures actinide complexes this type for An = Th, Pa, U, Np, Pu, Am. While 6d orbital is found to accommodate unpaired spin in species, next member series, characterized by an f2 ground state, later actinides successively fill 5f shell. In report, we principally examine evolution bonding as one advances along row. We find that early...

Addition of the Wittig reagent Ph(3)P═CH(2) to U(III) tris(amide) U(NR(2))(3) (R = SiMe(3)) generates a mixture products from which U(IV) complex U═CHPPh(3)(NR(2))(3) (2) can be obtained. Complex 2 features short U═C bond and represents rare example uranium carbene. In solution, exists in equilibrium with metallacycle U(CH(2)SiMe(2)NR)(NR(2))(2) free Ph(3)P═CH(2). Measurement this as function temperature provides ΔH(rxn) 11 kcal/mol ΔS(rxn) 31 eu. Additionally, electronic structure was...

Manipulation of steric crowding in organoactinide complexes has been explored by examining the insertion chemistry carbodiimides, RN═C═NR, and organic azides, RN3, with actinide alkyl, alkynyl, aryl complexes. iPrN═C═NiPr reacts (C5Me5)2AnMe2 to produce isomorphous methyl amidinates (C5Me5)2AnMe[(iPr)NC(Me)N(iPr)-κ2N,N′], An = Th, 1; U, 2, high yield. The reaction (C5Me5)2U(C≡CPh)2 forms a similar product, (C5Me5)2U(C≡CPh)[(iPr)NC(C≡CPh)N(iPr)-κ2N,N′], 3. (C5Me5)2U(C6H5)2 does not generate...

Oxidation of [Li(DME)(3)][U(CH(2)SiMe(3))(5)] with 0.5 equiv I(2), followed by immediate addition LiCH(2)SiMe(3), affords the high-valent homoleptic U(V) alkyl complex [Li(THF)(4)][U(CH(2)SiMe(3))(6)] (1) in 82% yield. In solid-state, 1 adopts an octahedral geometry as shown X-ray crystallographic analysis. Addition 2 tert-butanol to generates heteroleptic U(IV) [Li(DME)(3)][U(O(t)Bu)(2)(CH(2)SiMe(3))(3)] (2) high Treatment AgOTf fails produce a derivative, but instead...

The synthesis and structural determination of the first thorium phosphinidene complex are reported. reaction 2 equiv (C5Me5)2Th(CH3)2 with H2P(2,4,6-(i)Pr3C6H2) at 95 °C produces [(C5Me5)2Th]2(μ2-P[(2,6-CH2CHCH3)2-4-(i)PrC6H2] as well 4 methane, from deprotonation phosphine C-H bond activation one methyl group each isopropyl groups 2- 6-positions. Transition state calculations indicate that steps in mechanism P-H, C-H, then P-H to form phosphinidene.

The uranium(IV) terminal oxo species Tp*(2)U(O) has been synthesized by oxygen-atom transfer from pyridine-N-oxide to Tp*(2)U(2,2'-bipyridine), a trivalent uranium with monoanionic bipyridine ligand. Full characterization of the using (1)H NMR and IR spectroscopies, X-ray crystallography, computational studies was performed.

Hydrogenolysis of the dimethyl actinide metallocenes (C5Me4SiMe3)2UMe2 and (C5Me4H)2AnMe2 (An = Th, U) was examined for comparison with hydrogenolysis (C5Me5)2AnMe2 that forms hydrides [(C5Me5)2ThH2]2, [(C5Me5)2UH2]2, [(C5Me5)2UH]2. Parallel reactivity is not found (C5Me4SiMe3)− (C5Me4H)− complexes. Instead, this study led to first example a "tuck-over" [μ-η5-C5Me3H(CH2)-κC]2– dianion derived from ligands by C–H bond activation rare examples polymetallic thorium polyhydride compound an...

The synthesis and characterization of new Mn(I)- Re(I)-centered organometallic complexes fashioned with 1,4-diazabutadiene (DAB) ligands is reported. Ten compounds the type fac-(α-diimine)M(CO)3Br (M = Mn, Re) were obtained in moderate to excellent yield (35–80%) high purity from coordination five M(CO)5Br refluxing ethanol. Despite electronic similarity DAB 2,2′-bipyridyl, described herein poor mediators electrochemical CO2 conversion CO, but provide insight into role redox-active...

Dinuclear Cu(I) and Ag(I) complexes, Cu2[(2,6-Me2C6H3N)2C(H)]2, 1, Ag2[(2,6-Me2C6H3N)2C(H)]2, 2, Cu2[2,6-iPr2C6H3N)2C(H)]2, 3, Ag2[(2,6-iPr2C6H3N)2C(H)]2, 4, were synthesized from reactions of [Cu(NCCH3)4][PF6] with Na[(2,6-R2C6H3N)2C(H)] AgO2CCH3 [Et3NH][(2,6-R2C6H3N2C(H)], R = Me, iPr. Carbon disulfide was observed to insert into the metal–nitrogen bonds 1 produce Cu4[CS2(2,6-Me2C6H3NC(H)═NC6H3Me2)]4, 5, a Cu4S8 core, which represents rare transformation dinuclear tetranuclear species....

The insertion reactivity of (C5Me5)2U(C≡CPh)2, 1, has been studied with CO2, PhNCO, Me3CC≡N, and Me3CN≡C. Insertion into both U−C≡CPh bonds 1 occurs the first three substrates to form (C5Me5)2U(O2CC≡CPh)2, 2, (C5Me5)2U[PhNC(C≡CPh)O-κ2N,O]2, 3, (C5Me5)2U[N═C(CMe3)(C≡CPh)]2, 4, respectively. Only equiv Me3CN≡C reacts (C5Me5)2[(PhC≡C)C═N(CMe3)-η2C,N]U(C≡CPh), 5, a result similar iPrN═C═NiPr that forms (C5Me5)2[iPrNC(C≡CPh)NiPr-κ2N,N′]U(C≡CPh), 6.

Homoleptic soft-donor actinide complexes of the general form An[E2PROR′]4 were synthesized from salt metathesis between ThCl4(DME)2 or UI4(1,4-dioxane)2 and M[E2PROR′], M = Na, K, to yield 2 (An Th, E S, R 4-MeOC6H4, R′ Me), 3 tBu), 4 U, 5 Se, C6H5, 6 Me). In addition thorium uranium thioselenophosphinate 7 8 produced reaction Na[SSePPh2], respectively. All compounds characterized using elemental analysis, 1H 31P NMR, IR spectroscopy, U(IV) also examined with UV–vis spectroscopy. The 77Se...

This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with pioneering work Gilman during Manhattan project. The initial reports in this area suggested that uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated tractable could generated by purposeful "ate" complex formation, which serves saturate coordination sphere and provide complexes greater kinetic stability. More recently, we reported solid-state molecular structures...

Herein we report the synthesis and spectroscopic observation of a Pt complex featuring P2Si═ ligand containing central silylene donor connected to phosphines via two o-arylene linkers. Species type (P2Si═)PtR undergo net 1,2-migration R from Si, which leads highly unsaturated cations displaying only very distant interaction with weakly coordinating carborane anion.

The reactivity of thorium-phosphido and thorium-arsenido bonds was probed using tert-butyl isocyanide, (t)BuNC. Reaction (C5Me5)2Th[E(H)R]2, E = P, As; R 2,4,6-(i)Pr3C6H2, 2,4,6-Me3C6H2 with (t)BuNC affords the first phosphaazaallene arsaazaallene moieties an f-element.

Syntheses of rare examples U(V) methyl and U(IV) ylide complexes are reported. Reaction the previously reported imido complex [(C5Me5)2U(py)(═NMes)] (py = pyridine, Mes 2,4,6-Me3C6H2) with CuI forms [(C5Me5)2U(I)(═NMes)]. iodo MgMe2 produces [(C5Me5)2U(CH3)(═NMes)]. The was reacted CH2PPh3, surprisingly forming [(C5Me5)2U(CH2PPh3)(═NMes)], a ylide. This is formed from disproportionation transient carbene, leading to U(VI) bis(imido) complex, [(C5Me5)2U(═NMes)2]. These were characterized...

The reductive chemistry of U3+ in the metallocene amidinate coordination environment (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U, 1, has been explored. Two equivalents 1 react with PhSSPh and 2,2′-dithiopyridine (pySSpy) to produce (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(SPh), 2, (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(Spy), 3, respectively. Complexes 2 3 can also be synthesized through insertion iPrN═C═NiPr into methyl group (C5Me5)2UMe(SPh) (C5Me5)2UMe(Spy), 4, Complex readily reduces Cu1+ reagents, CuBr, CuI,...

Rare stakes: Terminal uranium(IV) disulfido and diselenido compounds, Tp*2U(E2) (ES, Se), were synthesized by the activation of elemental chalcogens (see figure). Structural, spectroscopic, computational magnetic studies these species establish their tetravalency highly polarized UE bonds. As a service to our authors readers, this journal provides supporting information supplied authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or...

Abstract As the reactivity of transition‐metal complexes with redox‐active ligands has gained significant attention in recent years, we have begun expanding to actinides. Here, report synthesis, characterization, and ( Mes DAB Me ) 2 Th(THF) { 1 , = [MesNC(Me)=C(Me)NMes] 2– 2,4,6‐trimethylphenyl, THF tetrahydrofuran}, which cleaves C–I bond CH 3 I subsequent Th–I C–C formation produce )( )ThI [MesN=C(Me)C(Me) NMes] – }. When is crystallized acetonitrile, solvated adduct )ThI(NCCH ‐MeCN)...

We report a comparison of the molecular and electronic structures dithio- diselenophosphinate, (E2PR2)1– (E = S, Se; R iPr, tBu), with thorium(IV) uranium(IV) complexes. For thorium dithiophosphinate complexes, reaction ThCl4(DME)2 4 equiv KS2PR2 (R tBu) produced homoleptic Th(S2PiPr2)4 (1S-Th-iPr) Th(S2PtBu2)4 (2S-Th-tBu). The diselenophosphinate complexes were synthesized in similar manner using KSe2PR2 to produce Th(Se2PiPr2)4 (1Se-Th-iPr) Th(Se2PtBu2)4 (2Se-Th-tBu). U(S2PiPr2)4,...

The complexes (C5 Me5 )2 Th(EHTipp)2 , (E=P or As; Tipp=2,4,6-triisopropylphenyl), provide a ligand framework that results in facile access to rare Th-E multiple bonds. reaction of with KN(SiMe3 proceeds cleanly the desired bridging phosphinidiide arsinidiide complex, [{(C5 Th(μ2 -ETipp)(μ2 -EHTipp)}K]2 under ambient conditions. In absence chelating agent, potassium cation one monomeric unit interacts aryl ring second monomer form bridged dimer. presence 2,2,2-cryptand, terminal...

The first uranium(iii) phosphido complex is reported. reaction of (C5Me5)2UI(THF) with KP[(C6H2Me3-2,4,6)(SiMe3)] affords (C5Me5)2U[P(C6H2Me3-2,4,6)(SiMe3)](THF), 1. reactivity 1 was explored two equivalents N3SiMe3 and N3Ad, Ad = adamantyl, both which produce U(vi) bis(imido) complexes via four-electron reduction the azides.

Chemical signatures correlated with uranium oxide processing are of interest to forensic science for inferring sample provenance. Identification temporal changes in chemical structures process materials as a function controlled temperatures and relative humidities may provide additional information regarding history. In this study, high-purity α-U3O8 three other samples synthesized from reaction routes used nuclear conversion processes were stored under conditions over 2-3.5 years, powder...