Magnetically Induced Amination of Alcohols Using MNi@Cu (M=Fe, Co) Nanoparticles as Catalysts.

The synthesis of tertiary amines from alcohols (i.e. heptanol, dodecanol, cyclohexanol, benzylalcohol) and secondary amines (MeNH (DMA), PrNH, BuNH) has been achieved in one step using trimetallic nanoparticles (NPs) displaying a magnetic core (CoNi and FeNi) and a Cu shell as both catalysts and heating agent in the presence of an alternating magnetic field.

Half-Sandwich Zirconium and Hafnium Amidoborane Complexes: Precursors of Hydride Derivatives.

Half-sandwich zirconium(IV) and hafnium(IV) complexes with amidoborane and hydride ligands have been isolated in the stoichiometric reactions of mono(pentamethylcyclopentadienyl)metal alkyl and amido derivatives with the amine-boranes NHRBH (R = H, Me, HBu). Treatment of the tris(trimethylsilylmethyl) complexes [M(η-CMe)(CHSiMe)] with NHBH (3 equiv) gives the seven-coordinate species [M(η-CMe)(NHBH)] (M = Zr (), Hf ()) with three κ-NHBH ligands. The tris(neophyl) [M(η-CMe)(CHCMePh)] or tris(dimethylamido) [M(η-CMe)(NMe)] derivatives react with NHMeBH (≥3 equiv) to afford bis(dimethylamidoborane) hydride complexes [M(η-CMe)H(NMeBH)] (M = Zr (), Hf ()) via thermally unstable [M(η-CMe)(NMeBH)] species.

Induction heating: an efficient methodology for the synthesis of functional core-shell nanoparticles.

Induction heating has been applied for a variety of purposes over the years, including hyperthermia-induced cell death, industrial manufacturing, and heterogeneous catalysis. However, its potential in materials synthesis has not been extensively studied. Herein, we have demonstrated magnetic induction heating-assisted synthesis of core-shell nanoparticles starting from a magnetic core.

Rhodium Complexes in P-C Bond Formation: Key Role of a Hydrido Ligand.

Olefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves the formation of P-C and H-C bonds. Thus, complexes that contain both hydrido and phosphanido functionalities are of great interest for the development of effective and fast catalysts.

Correction: Heterobimetallic ruthenium-zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity.

Correction for 'Heterobimetallic ruthenium-zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity' by Maialen Espinal-Viguri et al., Dalton Trans., 2019, 48, 4176-4189, DOI: 10.

Three-Coordinate Rhodium Complexes in Low Oxidation States.

The isolation of simultaneously low-coordinate and low-valent compounds is a timeless challenge for preparative chemists. This work showcases the preparation and full characterization of tri-coordinate rhodium(-I) and rhodium(0) complexes as well as a rare rhodium(I) complex. Reduction of [{Rh(μ-Cl)(IPr)(dvtms)} ] (1, IPr=1,3-bis(2,6-diisopropylphenyl)imidazolyl-2-ylidene; dvtms=divinyltetramethyldisiloxane) with KC gave the trigonal complexes K[Rh(IPr)(dvtms)] and [Rh(IPr)(dvtms)], whereas the cation [Rh(IPr)(dvtms)] results from their oxidation or by abstraction of chloride from 1 with silver salts.

Rhodium Complexes in P-H Bond Activation Reactions.

The feasibility of oxidative addition of the P-H bond of PHPh to a series of rhodium complexes to give mononuclear hydrido-phosphanido complexes has been analyzed. Three main scenarios have been found depending on the nature of the L ligand added to [Rh(Tp)(C H )(PHPh )] (Tp= hydridotris(pyrazolyl)borate): i) clean and quantitative reactions to terminal hydrido-phosphanido complexes [RhTp(H)(PPh )(L)] (L=PMe , PMe Ph and PHPh ), ii) equilibria between Rh and Rh species: [RhTp(H)(PPh )(L)]⇄[RhTp(PHPh )(L)] (L=PMePh , PPh ) and iii) a simple ethylene replacement to give the rhodium(I) complexes [Rh(κ -Tp)(L)(PHPh )] (L=NHCs-type ligands). The position of the P-H oxidative addition-reductive elimination equilibrium is mainly determined by sterics influencing the entropy contribution of the reaction.

Heterobimetallic ruthenium-zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity.

The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)'(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(η2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the coordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products.

Group 4 Half-Sandwich Tris(trimethylsilylmethyl) Complexes: Thermal Decomposition and Reactivity with N,N-Dimethylamine-Borane.

The thermal decomposition of group 4 trimethylsilylmethyl derivatives [M(η-CMe)(CHSiMe)] (M = Ti (1), Zr (2), Hf (3)) in solution and their reactivity with N,N-dimethylamine-borane were investigated. Heating of hydrocarbon solutions of compounds 2 and 3 at 130-200 °C results in the elimination of SiMe and the clean formation of the singular alkylidene-alkylidyne zirconium and hafnium compounds [{M(η-CMe)}{(μ-CH)SiMe}(μ-CSiMe)] (M = Zr (4), Hf (5)). The reaction of 2 and 3 with NHMeBH (≥1 equiv) at room temperature affords the dialkyl(dimethylamidoborane) complexes [M(η-CMe)(CHSiMe)(NMeBH)] (M = Zr (6), Hf (7)).

Crystal structure of (1,3-di-tert-butyl-η(5)-cyclo-penta-dien-yl)tri-methyl-hafnium(IV).

The mol-ecule of the title organometallic hafnium(IV) com-pound, [Hf(CH3)3(C13H21)] or [HfMe3(η(5)-C5H3-1,3- (t) Bu2)], adopts the classical three-legged piano-stool geometry for mono-cyclo-penta-dienylhafnium(IV) derivatives with the three methyl groups bonded to the Hf(IV) atom at the legs. The C atoms of the two tert-butyl group bonded to the cyclo-penta-dienyl (Cp) ring are 0.132 (5) and 0.

Heterometallic complexes with cube-type [MTi3N4] cores containing Group 10 metals in a variety of oxidation states.

Treatment of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] (1) with one equivalent of [Ni(cod)2] (cod = 1,5-cyclooctadiene) in toluene at 60–80 °C and subsequent addition of diphenylacetylene, trans-stilbene or triphenylphosphane afforded the nickel(0) complexes [LNi{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (L = PhCCPh (2), PhCH≡CHPh (3), PPh3 (4)). The nickel(II) complex [I2Ni{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (5) was prepared by analogous addition of iodine to the solution obtained from the heating of 1 and [Ni(cod)2]. Treatment of 1 with one equivalent of [Pd(dba)2] (dba = dibenzylideneacetone) in toluene at room temperature led to the palladium(0) complex [(dba)Pd{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (6).