Molecular Phosphide Complexes of Zirconium

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Molecular ZrIV phosphides are extremely rare, with no examples containing a one-coordinated and terminal triple-bonded phosphorus atom. We report here an isolable relatively stable Zr phosphide complex, [(PN)2Zr≡P{μ2-Na(OEt2)}]2 (4), stemming from cyclometalated Zr-hydride, [(PN)(PN')Zr(H)] (2), NaPH2. Complex 2 is prepared two- or one-electron reductions of precursors [(PN)2ZrCl2] (1) metastable ZrIII[(PN)2ZrCl], respectively. Oxidation ClCPh3 (2 equiv) I2 (1 resulted in re-formation the PN ligand isolation complexes [(PN)2ZrX2] (X = Cl, 1; X I, 3), whereas addition weak acid to allowed us intercept hydrido-halide intermediate [(PN)2Zr(I)(H)] I) spectroscopically before conversion 1 3. exchanged D2 atm) fully deuterate methylene all ortho-methyl groups PN' ligands hydride. Discrete salts 4 can be readily Na+ encapsulation crown ether 1,4,7,10,13,16-hexaoxacyclooctadecane (18-C-6) cryptand 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (222-Kryptofix) form [Na(18-C-6)(THF)2][(PN)2Zr≡P] (5) [Na(222-Kryptofix)][(PN)2Zr≡P] (6), respectively, which were structurally characterized. Compounds 4-6 demonstrate exceptionally short Zr≡P bonds (4, 2.3270(18) Å; 5, 2.291(3) 6, 2.2989(17) Å) highly downfield 31P NMR spectral resonances 819 ppm; 5 927 955 ppm) accord ligand. The motif stabilized via coordination softer Tl+ ion nonsolvated [(PN)2Zr≡P{μ2-Tl}]2 (7), exhibiting resonance at ∼711 ppm.

Язык: Английский

---

ThCTi@C_s(6)-C₈₂: Th═C Double Bond in a Mixed Actinide-Transition Metal Cluster

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

A thorium–carbon double bond that corresponds to the sum of theoretical covalent radii has long been sought after in study actinide-ligand multiple bonding as a synthetic target. However, stabilization this chemical remains great challenge date, part because relatively poor energetic matching between 5f-/6d- orbitals thorium and 2s-/2p- frontier carbon. Herein, we report successful synthesis carbon-bridged actinide-transition metal cluster, i.e., [Th═C═Ti], encapsulated inside fullerene cage C82. ThCTi@Cs(6)-C82 was successfully synthesized by modified arc discharging method characterized mass spectrometry, single-crystal X-ray crystallography, various spectroscopy, calculations. crystallographic analysis reveals bent μ2-bridged carbide cluster with Th–C distance 2.123(18) Å, which is shortest reported date an isolable compound comparable Th═C (2.10 Å). In addition, Th═C═Ti takes unexpected nonlinear configuration angle 133.0(10)°. The combined experimental investigation further revealed nature Th═C, polarized toward bridged carbon but notably higher covalency than bonds previously for organometallic compounds. Moreover, pronounced cage-to-metal donation appears be stabilizing cluster. This work offers deeper understanding behavior features unique ability cages stabilize motifs containing different types metal–ligand bonds.

Язык: Английский

---

Dipnictogen Radical Chemistry: A Dithorium-Supported Distibene Radical Trianion

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Although two examples of σ-bonded trans-bent [RSbSbR]•– (R = bulky organo- or Ga-groups) that formally contain the Sb2•3– radical trianion moiety are known in p-block chemistry, d- f-element complexes, with without R-substituents, have remained elusive. Here, we report reduction a 77:23 mix [{Th(TrenTIPS)}2(μ-η2:η2-Sb2)] (3a, TrenTIPS {N(CH2CH2NSiPri3)3}3–):[{Th(TrenTIPS)}2(μ-SbH)] (3b) 1.5 equiv KC8 presence 1.1 2.2.2-cryptand yields emerald green complex [K(2.2.2-cryptand)][{Th(TrenTIPS)}2(μ-η2:η2-Sb2)] (4), providing an f-block complex, and heaviest actinide-N2 analogue. When recrystallization conditions modified, small crop red crystals determined to be [K(2.2.2-cryptand)]3[{Th(TrenTIPS)(μ-η3:η3-Sb3)}2(μ-K)] (5) were also isolated, highlighting complexity heavy group 15 homodiatomic chemistry. SQUID magnetometry EPR spectroscopy suggest 4 is fairly well due electrostatic binding Th, pseudoaxial g-values reflecting distinctive side-on bridging π-bonded coordination mode. Spectroscopically validated computational analysis 3a confirms stronger donating capability, weaker Sb–Sb bond, compared Sb22– dianion form.

Язык: Английский

---

Transient Triplet Metallopnictinidenes M–Pn (M = Pd^II, Pt^II; Pn = P, As, Sb): Characterization and Dimerization

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity this important class transient intermediates has attributed their electronic structures, particularly the accessibility triplet vs singlet states. In contrast, structure trends along heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report synthesis series metallodipnictenes, {M–Pn═Pn–M} (M PdII, PtII; P, As, Sb, Bi) characterization metallopnictinidene intermediates, {M–Pn} for Sb. Structural, spectroscopic, computational analysis revealed spin ground states metallopnictinidenes with characteristic series. comparison nitrene, pnictinidenes exhibit lower-lying state SOMOs excited states, thus suggesting increased electrophilic reactivity. Furthermore, splitting magnetic microstates is beyond phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Язык: Английский

---

Electronic Delocalization and σ-Aromaticity in Heterometallic Cluster with Multiple Thorium–Palladium Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12790 - 12798

Опубликована: Апрель 29, 2024

Research on metal–metal bonds involving f-block actinides, such as thorium, lags far behind the well-studied of d-block transition metals. The complexes with Th–TM are extremely rare; all previously identified examples have only a single bond Th center at an invariably +IV oxidation state. Herein, we report series Th2Pdn (n = 2, 3, and 6) clusters (complexes 4, 7) multiple Th(III)–Pd bonds. Theoretical studies reveal that unit allows electronic delocalization σ aromaticity, leading to unexpected closed-shell singlet structures for these Th(III) species. This is evident in highest occupied molecular orbital facilitates 2e reduction alkyne by complex 7, resulting formation 8. Complexes 7 8 distinctive featuring Th2Pd6 core six eight Th–Pd bonds, respectively, making them largest known d–f heterometallic exhibiting bonding.

Язык: Английский

---

Heterometallic Clusters with Thorium–Rhodium Bonds Supported by Double-Layer Nitrogen–Phosphorus Ligands

Organometallics, Год журнала: 2025, Номер 44(1), С. 354 - 362

Опубликована: Янв. 1, 2025

The investigation of metal–metal bonds involving f-block actinides has significantly lagged behind extensive research on d-block transition metal bonds. Species featuring thorium-transition are exceptionally rare. In this study, we report the synthesis first species containing Th–Rh Using two nitrogen–phosphorus ligands, [CH3N(CH2CH2NHPiPr2)2] and {[CH2O(CH2)2NHPiPr2]2}, synthesized Th(IV) chloride precursors 1 5. Reactions precursor with [RhCl(COD)]2 or [IrCl(COD)]2 at room temperature produced heterometallic clusters 2 3, respectively. Similarly, 5 reacted under same conditions to yield analogues 6 7. Notably, heating complexes 90 °C led formation 4 8, each bonding interactions. interaction in complex 8 is stronger than that 7, as confirmed by both experimental observations theoretical analysis.

Язык: Английский

---

Trendbericht Anorganische Chemie 2024: Nebengruppen‐ und Koordinationschemie

Nachrichten aus der Chemie, Год журнала: 2025, Номер 73(2), С. 56 - 64

Опубликована: Янв. 31, 2025

Abstract Das erste heterobimetallische Dimetallocen; mit sterisch anspruchsvollen Liganden lassen sich einfach‐koordinierte Hauptgruppenverbindungen der Gruppen 13 bis 15 herstellen; neue Diazoverbindungen erlauben es, B‐R‐Einheiten und Kohlenstoffatome zu übertragen.

---

Arene-, Chlorido-, and Imido-Uranium Bis- and Tris(boryloxide) Complexes

Inorganic Chemistry, Год журнала: 2024, Номер 63(21), С. 9588 - 9601

Опубликована: Апрель 1, 2024

We introduce the boryloxide ligand {(HCNDipp)2BO}− (NBODipp, Dipp = 2,6-di-isopropylphenyl) to actinide chemistry. Protonolysis of [U{N(SiMe3)2}3] with 3 equiv NBODippH produced uranium(III) tris(boryloxide) complex [U(NBODipp)3] (1). In contrast, treatment UCl4 NBODippK in THF at room temperature or reflux conditions only [U(NBODipp)2(Cl)2(THF)2] (2) 1 remaining unreacted. However, refluxing mixture 2 and unreacted toluene instead afforded target [U(NBODipp)3(Cl)(THF)] (3). Two-electron oxidation AdN3 (Ad 1-adamantyl) uranium(V)–imido [U(NBODipp)3(NAd)] (4). The solid-state structure reveals a uranium–arene bonding motif, structural, spectroscopic, DFT calculations all suggest modest δ-back-bonding approximately equal donation into arene π4 π5 δ-symmetry π* molecular orbitals. Complex 4 exhibits short distance, computational modeling enabled its electronic be compared related uranium–imido uranium–oxo complexes, revealing substantial 5f-orbital crystal field splitting extensive mixing 5f |ml,ms⟩ states mj projections. Complexes 1–4 have been variously characterized by single-crystal X-ray diffraction, 1H NMR, IR, UV/vis/NIR, EPR spectroscopies, SQUID magnetometry, elemental analysis, CONDON, F-shell, DFT, NLMO, QTAIM quantum chemical calculations.

Язык: Английский

---

Heterodinuclear AuNi(CO)_n^– (n = 2–3) Complexes Featuring an Anionic Au^– as a Donor Ligand for Ni(CO)_n

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(33), С. 6917 - 6926

Опубликована: Авг. 12, 2024

The gas-phase heterodinuclear gold-nickel carbonyl AuNi(CO)

Язык: Английский

---

Fluoride Clusterfullerenes: Tuning Metal–Metal Bonding and Magnetic Properties via Single Fluorine Atom Doping

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 7, 2024

Endohedral fullerenes are known for their exceptional ability to host metal clusters that contain unique bonding motifs. In this study, we report a facile strategy synthesize new family of clusterfullerenes, fluoride clusterfullerenes (FCFs). This work demonstrates actinides and rare earth metals as well alkaline can be encapsulated within variety fullerene cages, these obtained in pristine form without additional functionalization methods. Notably, Th

Язык: Английский

---