While β-diketiminate (BDI or ‘nacnac’) ligands have been widely adopted to stabilize a wide range of metal ions in multiple oxidation states and coordination numbers, several occurrences these do not behave as spectators participate reactivity.

Siloxides can support U! …︁in the reduction of small molecules with uranium complexes. The treatment [U{N(SiMe3)2}3] HOSi(OtBu)3 (3 equiv) yielded a novel homoleptic uranium(III) siloxide complex 1, which acted as two-electron reducing agent toward CS2 and CO2 (see scheme). Complex 1 also reduced toluene to afford diuranium inverted-sandwich complex. Detailed facts importance specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or...

The new homoleptic ate U(III) siloxide [K(18c6)][U(OSi(O(t)Bu)3)4] 2 was prepared in 69% yield by reduction of [U(OSi(O(t)Bu)3)4] 3 with KC8. reaction the neutral complex [U(OSi(O(t)Bu)3)2(μ-OSi(O(t)Bu)3)]2 1 adamantyl azide leads to isolation dinuclear U(VI) imido [U2(NAd)4(OSi(O(t)Bu)3)4] 4. X-ray crystal structure shows presence a "cation-cation interaction" between two [U(NAd)2](2+) groups. In contrast reactions trimethylsilyl and azides afford U(V) complexes...

The metal-mediated redox transformation of CO2 in mild conditions is an area great current interest. role cooperativity between a reduced metal center and Lewis acid small-molecule activation increasingly recognized, but has not so far been investigated for f-elements. Here we show that the presence potassium at U, K site supported by sterically demanding tris(tert-butoxy)siloxide ligands induces large cooperative effect reduction CO2. Specifically, ion pair complex...

New tris-amidinate actinide (Th, U) complexes containing a rare O-bound terminal phosphaethynolate (OCP - ) ligand were synthesized and fully characterized. The cyanate (OCN thiocyanate (SCN analogs prepared for comparison feature preferential N-coordination to the metals. Th(amid)3(OCP) complex reacts with Ni(COD)2 yield heterobimetallic adduct (amid) 3 Th(μ-η 1 (O):η 2 (C,P)-OCP)Ni(COD) featuring an unprecedented reduced bent fragment bridging two

A method for the synthesis of substituted cycloalkanes was developed using diols and secondary alcohols or ketones via a cascade hydrogen borrowing sequence. non-noble air-stable manganese catalyst (2 mol %) used to perform this transformation. Various 1,5-pentanediols (3-4 equiv) (1 were investigated prepare collection cyclohexanes in diastereoselective fashion. Similarly, cyclopentane, cyclohexane, cycloheptane rings constructed from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,...

The iridium tetrahydride complex Cp*IrH4 reacts with a range of isobutylaluminum derivatives general formula Al(iBu)x(OAr)3–x (x = 1, 2) to give the unusual aluminum species [Cp*IrH3Al(iBu)(OAr)] (1) via reductive elimination route. Lewis acidity Al atom in 1 is confirmed by coordination pyridine, leading adduct [Cp*IrH3Al(iBu)(OAr)(Py)] (2). Spectroscopic, crystallographic, and computational data support description these heterobimetallic complexes 2 as featuring strongly polarized...

We have developed a new way to introduce redox events at lanthanide centers which should lead further expansion of the reductive chemistry lanthanides.

The reaction of U(III) with Schiff base ligands and the reduction U(IV) complexes both promote C−C bond formation to afford dinuclear or mononuclear amido complexes, which can release up four electrons substrates through oxidative cleavage bond.

Two new arene inverted-sandwich complexes of uranium supported by siloxide ancillary ligands [K{U(OSi(OtBu)3)3}2(μ-η(6):η(6)-C7H8)] (3) and [K2{U(OSi(OtBu)3)3}2(μ-η(6):η(6)-C7H8)] (4) were synthesized the reduction parent arene-bridged complex [{U(OSi(OtBu)3)3}2(μ-η(6):η(6)-C7H8)] (2) with stoichiometric amounts KC8 yielding a rare family in three states charge. The structural data computational studies electronic structure are agreement presence high-valent centers bridged reduced...

The reaction of the tripodal tris-amido U(III) complex [U{(SiMe2NPh)3–tacn}] (tacn = 1,4,7-triazacyclononane), 1, with 0.0625 and 0.25 equiv. elemental sulfur affords sulfide-bridged U(IV) [{U((SiMe2NPh)3–tacn)}2(μ-S)], 2, terminal persulfide U(V) [U{(SiMe2NPh)3–tacn}(η2-S2)], 4, respectively, in good yield. Two different electronic structures, supersulfide, were computed for 4 at DFT level. results show that is best described as a species significant contribution. X-ray, magnetism...

The reactivity of cobalt complexes supported by a PNP pincer ligand towards H2 varies depending on whether the N-donor atom is protonated; synthesis [(HPNP)CoCl(H)2] (2), [(PNP)CoH]2 (4), and trihydride species [(HPNP)CoH3] (7) (HPNP = HN(CH2CH2PiPr2)2) are described.

We report the synthesis and comprehensive study of electronic structure a unique series dinuclear group 5 cyclo-tetraphosphide inverted sandwich complexes. White phosphorus (P4) reacts with niobium(III) tantalum(III) β-diketiminate (BDI) tert-butylimido complexes to produce bridging cyclo-P4 phosphide species {[(BDI)(NtBu)M]2(μ-η3:η3P4)} (1, M = Nb; 2, Ta) in fair yields. 1 is alternatively synthesized upon hydrogenolysis (BDI)Nb(NtBu)Me2 presence P4. The trinuclear side product...

A novel heterobimetallic tantalum/iridium hydrido complex, [{Ta(CH2tBu)3}{IrH2(Cp*)}] 1, featuring a very short metal-metal bond, has been isolated through an original alkane elimination route from Ta(CHtBu)(CH2tBu)3 and Cp*IrH4. This molecular precursor used to synthesize well-defined silica-supported low-coordinate species [≡SiOTa(CH2tBu)2{IrH2(Cp*)}], 5, [≡SiOTa(CH2tBu)H{IrH2(Cp*)}], 6, using surface organometallic chemistry (SOMC) approach. The SOMC methodology prevents undesired...

The activation of C–H bonds by heterobimetallic compounds is a rich area research that has recently received increased attention. This perspective highlights recent advances and aims to guide the reader in this rapidly evolving field.

A Surface OrganoMetallic Chemistry (SOMC) approach is used to prepare a novel hafnium-iridium catalyst immobilized on silica, HfIr/SiO

The straightforward synthesis of a new unsymmetrical hydroxy-tethered N-heterocyclic carbene (NHC) ligand, HL, is presented. free ligand exhibits an unusual OH-carbene hydrogen-bonding interaction. This motif was used to yield 1) the first tantalum complex displaying both Fischer- and Schrock-type 2) unique NHC-based early/late heterobimetallic complex. More specifically, protonolysis chemistry between ligand's hydroxy group imido-alkyl or alkylidene-alkyl precursor complexes yielded rare...

A highly efficient catalyst–base pair for the C–H arylation of free (NH)-indoles in C-3 position is reported. Ligand-free palladium acetate coupled with lithium hexamethyldisilazide (LiHMDS) catalyzed regiospecific, i.e. 100% regioselective, indoles high turnover numbers. This catalytic system has been successfully applied to a wide range substrates, including various functional aryl halides and indolic cores. The unique role LiHMDS as both base unexpected transient directing group revealed...

Siloxide unterstützen die Reduktion kleiner Moleküle durch Uran-Komplexe. Die Behandlung von [U{N(SiMe3)2}3] mit HOSi(OtBu)3 (3 Äquiv.) liefert den neuartigen homoleptischen Uran(III)-Siloxid-Komplex 1, der als Zwei-Elektronen-Reduktionsmittel für CS2 und CO2 (siehe Schema) wirkt. Komplex 1 reduziert außerdem Toluol bildet einen invertierten Diuran-Sandwichkomplex. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but...

The synthesis, structure, and reactivity of a new complex U(IV) with the tridentate Schiff base ligand Menaphtquinolen are reported. reduction bis-ligand complexes [UX2(Menaphtquinolen)2] (X = Cl, (1-Cl) ; I (1-I)) potassium metal affords tetranionic hexadentate μ-bis-Menaphtquinolen formed through intramolecular reductive coupling imino groups each unit. solid state structure [U(μ-bis-Menaphtquinolen)]2 dimer 2 isolated from toluene confirms presence reduced ligand. Reactivity studies...

The homoleptic compounds [U(salan-R2)2] (R = Me (1), tBu (2)) were prepared in high yield by salt-metathesis reactions between UI4(L)2 (L Et2O, PhCN) and 2 equiv of [K2(salan-R2)] THF. In contrast, the reaction tetradentate ligands salan-R2 with UI3(THF)4 leads to disproportionation metal mixtures U(IV) [U(salan-R2)I2] complexes, depending on ligand M ratio. K2salan-Me2 iodide chloride salts always bis-ligand complex [U(salan-Me2)2] heteroleptic complexes [U(salan-Me2)X2] different organic...

Uranyl(VI), uranyl(V), and uranium(IV) complexes supported by ferrocene-based tetradentate Schiff-base ligands were synthesized, their solid-state solution structures determined. The redox properties of all investigated cyclic voltammetry. bulky salfen-(t)Bu2 allows the preparation a stable uranyl(V) complex, while U(IV) bis-ligand complex is obtained from salt metathesis reaction between [UI4(OEt2)2] K2salfen. reduction [U(salfen)2] leads to an unprecedented intramolecular reductive...

The low temperature regioselective hydrosilylation of various alkenes with (1,1,1,3,5,5,5-heptamethyltrisiloxane) MDHM is described using Mn2(CO)10 under UV irradiation Mn loadings as 1 mol%, in the absence additives and excellent selectivity yields. generation a manganese radical allowed anti-Markovnikov products to be selectively obtained yields up 99%.

We report an original alkane elimination approach, entailing the protonolysis of triisobutylaluminum by acidic hydrides from Cp*IrH4. This strategy allows access to a series well-defined tri- and tetranuclear iridium aluminum polyhydride clusters, depending on stoichiometry: [Cp*IrH3Al(iBu)2]2 (1), [Cp*IrH2Al(iBu)]2 (2), [(Cp*IrH3)2Al(iBu)] (3), [(Cp*IrH3)3Al] (4). Contrary most transition-metal aluminohydride complexes, which can be considered as [AlHx+3]x- aluminates LnM+ moieties,...