Stabilisation of a Strontium Hydride with a Monodentate Carbazolyl Ligand and its Reactivity.

Angew Chem Int Ed Engl

Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Geb. 30.45, Karlsruhe, Germany.

Published: November 2024

The molecular strontium hydride 2 [(Cbz)SrH(L)] (L=benzene, toluene) was isolated and stabilized by employing a sterically demanding carbazole ligand (Cbz=1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazolyl). Compound 2 was synthesized via phenylsilane metathesis with the corresponding amide (Cbz)SrN(SiMe) and characterized by H NMR, XRD and vibrational spectroscopy methods. We further investigated the stoichiometric reactivity of 2 towards carbon monoxide, azobenzene and trimethylsilylacetylene, showing three distinct reactivity pathways: addition, reduction and deprotonation. The reaction of 2 with carbon monoxide yields the ethenediolate complex 4 via addition, while with azobenzene reduction of the N-N double bond and release of hydrogen were observed, affording a heteroleptic strontium complex with a radical azobenzenyl ligand (5). The terminal alkyne is deprotonated by the hydride moiety to give the acetylide complex 6.

Download full-text PDF

Source
http://dx.doi.org/10.1002/anie.202418558DOI Listing

Publication Analysis

Top Keywords

strontium hydride
8
carbon monoxide
8
stabilisation strontium
4
hydride monodentate
4
monodentate carbazolyl
4
carbazolyl ligand
4
ligand reactivity
4
reactivity molecular
4
molecular strontium
4
hydride [cbzsrhl]
4

Similar Publications

Stabilisation of a Strontium Hydride with a Monodentate Carbazolyl Ligand and its Reactivity.

Angew Chem Int Ed Engl

November 2024

Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Geb. 30.45, Karlsruhe, Germany.

The molecular strontium hydride 2 [(Cbz)SrH(L)] (L=benzene, toluene) was isolated and stabilized by employing a sterically demanding carbazole ligand (Cbz=1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazolyl). Compound 2 was synthesized via phenylsilane metathesis with the corresponding amide (Cbz)SrN(SiMe) and characterized by H NMR, XRD and vibrational spectroscopy methods. We further investigated the stoichiometric reactivity of 2 towards carbon monoxide, azobenzene and trimethylsilylacetylene, showing three distinct reactivity pathways: addition, reduction and deprotonation.

View Article and Find Full Text PDF

Reactivity of Strontium Hydride Supported by the Superbulky Hydrotris(pyrazolyl)borate Ligand.

Inorg Chem

October 2024

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, No. 5625 Renmin Street, Changchun 130022, China.

Hydrogenolysis of [(Tp)Sr{CH(SiMe)}] () (Tp = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) in hexane solution under 20 atm of H allowed for the isolation of strontium hydride [(Tp)Sr(μ-H)] () in good yield. Complex exhibits the dimeric nature in solid state, featuring two different bond modes between the Sr center and Tp ligand. Treatment of complex with PhC(H)═NBu or PhCHBpin (Bpin = pinacolateborane) afforded the strontium amide complex [(Tp)Sr{N(CHPh)(Bu)}] () and hydroborate complex [(Tp)Sr{μ-HBpin(CHPh)}] (), respectively.

View Article and Find Full Text PDF

A bulky, unsymmetrical β-diketiminate ligand, [HC{MeCN(Dip)}{MeCN(TCHP)}] (Nacnac; Dip = 2,6-diisopropylphenyl, TCHP = 2,4,6-tricyclohexylphenyl), has been utilised in the preparation of a series of magnesium alkyl and calcium, strontium and barium amide complexes. Reaction of these with PhSiH afforded the first complete series of β-diketiminato heavier group 2 metal hydride complexes, [{(Nacnac)M(μ-H)}] (M = Mg, Ca, Sr or Ba). The unsymmetrical nature of the β-diketiminate ligand seemingly promotes stabilising interactions of ligand Dip groups with the metal centres in the Ca, Sr and Ba hydride complexes.

View Article and Find Full Text PDF

Ammonia synthesis the catalytic Haber-Bosch process is characterized by its high pressures and low single-pass conversions, as well as by the energy-intensive production of the precursors H and N and their concomitant greenhouse gas emissions. Alternatively, thermochemical cycles based on metal nitrides stand as a promising pathway to green ammonia production because they can be conducted at moderate pressures without added catalysts and be further driven by concentrated solar energy as the source of high-temperature process heat. The ideal two-step cycle consists of the nitridation of a metal to form a metal nitride, followed by the hydrogenation of the metal nitride to synthetize NH and reform the metal.

View Article and Find Full Text PDF

Multianionic metal hydrides, which exhibit a wide variety of physical properties and complex structures, have recently attracted growing interest. Here we present Sr N[BN ] H , prepared in a solid-state ampoule reaction at 800 °C, as the first combination of nitridoborate, nitride and hydride anions within a single compound. The crystal structure was solved from single-crystal X-ray and neutron powder diffraction data in space group P2 /c (no.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!