Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 29, 2024

Abstract Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons transient phosphinidenes. However, the synthesis such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies phosphanorcaradiene, in which one benzene rings flanking fluorenyl substituents intramolecularly dearomatized through attachment atom. It facilely obtained by reduction phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts synthetic equivalent phosphinidene. reacts trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. When treated two molar equivalents azide, iminophosphane bis(imino)phosphane isolated, Moreover, capable activating ethylene alkyne afford [1 + 2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceed smoothly at room temperature without presence transition metals. The driving force for these most likely ring-constraint three-membered PC 2 ring recovery aromaticity ring.

Language: Английский

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A Lead(II) Substituted Triplet Carbene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29630 - 29636

Published: Oct. 18, 2024

Reaction of the pincer-type ligand L

Language: Английский

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Trendbericht Anorganische Chemie 2024: Hauptgruppen‐ und Molekülchemie

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(2), P. 46 - 55

Published: Jan. 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.

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A Spectroscopic Criterion for Identifying the Degree of Ground-Level Near-Degeneracy Derived from Effective Hamiltonian Analyses of Three-Coordinate Iron Complexes

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 1016 - 1030

Published: Feb. 6, 2025

The fascinating magnetic and catalytic properties of coordinatively unsaturated 3d metal complexes are a manifestation their electronic structures, in particular nearly doubly or triply degenerate orbital ground levels. Here, we propose criterion to determine the degree degeneracy this class based on experimentally accessible anisotropy (parametrized by electron spin g- zero-field splitting (ZFS)-tensors). is derived from comprehensive spectroscopic theoretical study trigonal planar iron(0) complex, [(IMes)Fe(dvtms)] (IMes = 1,3-di(2′,4′,6′-trimethylphenyl)imidazol-2-ylidene, dvtms divinyltetramethyldisiloxane, 1). Accurate ZFS-values (D +33.54 cm–1, E/D 0.09) g-values (g∥ 1.96, g⊥ 2.45) triplet (S 1) level complex 1 were determined complementary THz-EPR spectroscopy SQUID magnetometry. In-depth effective Hamiltonian (EH) analyses coupled wave-function-based ab initio calculations show that features with three energetically close-lying states "two-above-one" energy pattern. observed results mixing two excited state spin–orbit coupling (SOC). EH investigations related allowed us generalize finding establish ZFS-tensors as markers for assigning two- three-fold near-degeneracy.

Language: Английский

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Crystalline Arylstibinidene Chalcogenides: Heavier Congeners of Aromatic Nitroso Compounds

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Nitroso compounds, R-N═O, containing N═O double bonds are ubiquitous and widely utilized in organic synthesis. In contrast, heavier congeners of nitroso namely pnictinidene chalcogenides R-Pn = E (Pn P, As, Sb, Bi; O, S, Se, Te), highly reactive scarce. They have been stabilized the coordination sphere Lewis acid/base or by pronounced contribution from resonance structures, whereas free species with unperturbed pnictogen-chalcogen remains elusive. this work, we report isolation characterization arylstibinidene chalcogenides, which first aromatic compounds. facilely synthesized through salt metathesis reactions aryldichlorostibane dilithium chalcogenides. bear Sb═E (E Se Te) due to poor orbital overlap between C 2p orbitals phenyl ring substituent Sb 5p orbitals. Moreover, they show versatile reactivity, including acting as chalcogen atom transfer reagents reacting small molecules via (cyclo)addition.

Language: Английский

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Isolation of Silylene-Ligated Plumbyliumylidene and Diplumbyne

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Language: Английский

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A singly bonded gallanediyl with redox-active and redox-inert reactivity

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

Language: Английский

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Synthesis and Characterization of Diarylgermanethione and Diarylgermaneselenone

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(34)

Published: Sept. 30, 2024

Abstract Lewis acid/base‐free diarylgermanethione 3 and diarylgermaneselenone 4 were synthesized through reactions of a heteroleptic diarylgermylene with elemental sulfur selenium, respectively. They fully characterized by structural, spectroscopic computational methods. Germanethione underwent 1,2‐addition AlMe at the Ge=S double to give Ge(IV) compound 5 . The chalcogen atoms in could coordinate copper halide yield Cu(I) complexes 6 7 ,

Language: Английский

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Philip P. Power: Celebrating a Career in Exploratory Synthesis

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(52), P. 24445 - 24452

Published: Dec. 30, 2024

InfoMetricsFiguresRef. Inorganic ChemistryVol 63/Issue 52Article This publication is free to access through this site. Learn More CiteCitationCitation and abstractCitation referencesMore citation options ShareShare onFacebookX (Twitter)WeChatLinkedInRedditEmailJump toExpandCollapse EditorialDecember 30, 2024Philip P. Power: Celebrating a Career in Exploratory SynthesisClick copy article linkArticle link copied!Cary R. Stennett*Cary Stennett*[email protected]More by Cary Stennetthttps://orcid.org/0000-0002-2727-5747Joshua D. QueenJoshua QueenMore Joshua Queenhttps://orcid.org/0000-0002-6726-417XKarin RuhlandtKarin RuhlandtMore Karin RuhlandtYang PengYang PengMore Yang Penghttps://orcid.org/0000-0002-6780-2468Clifton L. WagnerClifton WagnerMore Clifton Wagnerhttps://orcid.org/0000-0002-8045-7777Open PDFInorganic ChemistryCite this: Inorg. Chem. 2024, 63, 52, 24445–24452Click citationCitation copied!https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c05302https://doi.org/10.1021/acs.inorgchem.4c05302Published December 2024 Publication History Received 12 2024Published online 30 issue 2024editorialCopyright © Published American Chemical Society. available under these Terms of Use. Request reuse permissionsThis licensed for personal use The ACS PublicationsCopyright SocietyEvery field science has among its ranks those researchers whose work so transformative, foundational, or broad scope that it challenge not cite their when writing manuscript. In the search new project research direction, frequently happens just one thinks they have next great idea, even brief review literature reveals another researcher already had same idea published result years prior. For working inorganic organometallic synthesis, major source variety frustration Philip Power.Phil was born spent his youth early adulthood County Cork, Ireland, earned undergraduate degree natural from University Dublin 1974. After briefly with David Cardin, he made pivotal decision study synthetic chemistry Michael F. Lappert at Sussex. There, studied spectroscopy low-coordinate low-valent complexes Group 14 15 elements stabilized sterically encumbering alkyl amide groups (1−6) D.Phil. 1977. He subsequently NMR crowded phosphines Harold Goldwhite California State University, Los Angeles, (7) after which joined laboratory Richard H. Holm Stanford where contributed very efforts synthetically molybdenum–iron–sulfur clusters as models active sites biological nitrogenases. (8−12)After appointment an assistant professor 1981 (UC) Davis, synthesis stable unusual valences coordination numbers would become dominant theme research. As happened, good fortune joining Chemistry Department UC Davis auspicious time. Substantial advances single-crystal X-ray diffractometry, particularly development rapid data collection cryogenic temperatures, (13) were being introduced member department, Håkon Hope. Later, fruitful relationships crystallographers Marilyn Olmstead Jim Fettinger, collaborations technological helped develop attitude toward crystallography "analysis first resort" became pervasive laboratory. (14) ready availability highly time, significant factor building culture ideas could be rapidly realized visualized. Thus, what began fundamental structural studies ways organolithium organocopper species aggregate solid state (15−20) ultimately career exploratory examined limit accessible molecular main-group transition metal chemistry.Phil's dedication resulted isolation many classes compounds other chemical "firsts", exhaustive description make excellent standalone volume. special issue, Highlights Molecular Main Chemistry, we collected 50 "favorite" articles greater than 300 contributions Society journals along several written former students, collaborators, colleagues. While nominally concerned chemistry, readers editorial will understand Phil's also includes metals (indeed, most cited paper concerns chromium complex displaying example quintuple bond molecule). (21)In addition scientific advances, Phil co-authored two books on topic (22,23) Editor-in-Chief Volume 37 Syntheses, (24) longtime associate editor Chemistry. such, authors Editorial like honor achievements during synthesis. Here, celebrate breadth impact discussing four distinct themes laboratory, although discussions are no means comprehensive.Early Advances Structural ChemistryClick section linkSection copied!As mentioned above, advent low-temperature crystallography, developed Hope, revolutionized chemistry. kind data, previously limited rather arduous process transferring air-sensitive inert gas into glass capillaries, dramatically improved ease structurally characterized. ability obtain air- moisture-sensitive crystals using oil mounting technique, protects crystalline samples exposure air against desolvation, only resulting quality but allowed unattainable sensitive including unstable ether solvates. It methods community, remain foundation analysis compounds.Phil's pioneering since demonstrated power demanding ligands stabilize centers, challenging previous thinking about bonding characteristics oxidation states transition-metal compounds. Furthermore, opened doors catalysis, newer showing certain can exhibit reactivity thought metals. (25)Early focused preparation reactive Lewis basic donors. 1985, group reported triphenylmethyl diphenylmethyl anions, authenticated examples carbanions. (26) collecting diffraction temperatures crown ethers provide coordinative stabilization cationic lithium center. (27) quick succession came demonstrating stabilizing low numbers, seen, example, series two-coordinate quasi-two-coordinate open-shell bearing borylamido ligands, (28) (at time) complexes, (29) three-coordinate manganese(III) cobalt(III) synthesized oxidative route involving reaction corresponding divalent amides M{N(SiMe3)2}2 BrN(SiMe3)2 (Figure 1). (30) pursuit open-shell, go area lab. Over collaborative profited greatly magnetic Gary Long (31,32) William Reiff (33,34) theoretical Shigeru Nagase. (35,36) Among exciting findings, showed experimentally relationship between L–M–L angles similar ligand sets moments.Figure 1Figure 1. manganese tris(silylamide) Mn{N(SiMe3)2}3 cobalt analogue, lab BrN(SiMe3)2, cobalt(III).High Resolution ImageDownload MS PowerPoint SlideThe unprecedented impressively 1993 J. Am. Soc describing donor solvent-free aryl species. (37) Sterically enabled avoidance donors, providing states. Such hallmark laboratory.A central been comparison heavy first-row analogues, once common belief multiple predominantly main group. One Power group's landmark papers report six-membered iminoalane [MeAlN(2,6-iPr2-C6H3)]3, featured aluminum nitrogen atoms, i.e., aluminum–nitrogen analogue borazine 2). (38) quickly followed heavier Ga3P3 ring system type [(2,4,6-Ph3-C6H2)GaP(cyclo-C6H11)]3. (39) core molecule consists exclusively elements, nonplanar arrangement atoms underlines differences light counterparts. Adding concept 13–15 number publications propensity p-block form bonds ethylene analogues. (40−42) With prepare unsolvated based quest further increase size established concepts led terphenyl system, tailored modification flanking phenyl substituents.Figure 2Figure 2. trimeric shown here, borazine, exemplary substituted engender steric congestion reduce (or eliminate) oligomerization ongoing laboratory.High SlideComplexes Terphenyl LigandsClick copied!A consistent bulky m-Terphenyls mainstay lab, convenient "one-pot" procedure initial m-terphenyl described Hart career. (43) methodology independently expanded upon adjustable electronic properties. demand rings prevented nonmetals key such alkyne analogues 13 (44) (45−47) homologous alkene elements. (48)With sufficient ligand, monomeric containing univalent, one-coordinate isolated gallium, (49) indium, (50) thallium, (51) eventually aluminum, (52) 3), while evidence transient univalent radical mount spectroscopic evidence. (53−56) attempts boron supported reductive activation products, (62) borylenes Braunschweig. (63) Photolysis thermolysis Cr(CO)5(BAr) (Ar = C6H3-2,6-(C6H2-2,4,6-iPr3)2 ":BAr" explored cycloaddition reactions (64) complexation CO isocyanide ligands. (65) A reports bismuth (57) Cornella antimony, (58) germanium, (59) tin, (60) lead (61) Tan crowding hydrindacene that, supporting radicals 4).Figure 3Figure 3. High permitted aluminum(I), gallium(I), indium(I), thallium(I).High SlideFigure 4Figure 4. Since here.High conversion parent aryls pnictogenide chalcogenide derivatives adjustment profiles. terphenylamide terphenylthiolate metal(II) vanadium(II) bisamide (36) thiolates Cr–Zn. (66) Work late Mark Niemeyer (a postdoctoral lab) extended lanthanides 5). (67−69) -thiolate recently proven successful yttrium, (70) lanthanides, (71,72) uranium. (73) iron dithiolate served useful reagents Fe4S4 clusters, complete [Fe4S4]4+/3+/2+/1+/0 relevant systems, due bind potassium countercations. (74)Figure 5Figure 5. "traditional" rare-earth M(II) secondary η6 interactions ligands.High SlideSmall-Molecule Activation Heavy Main-Group Element ComplexesClick our understanding Historically, broadly categorized Compounds defining characteristics: (1) characterized partially filled valence d orbitals, closely spaced energy, (2) often colored low-energy separations (3) interact small molecules carbon monoxide (CO), (C2H4), hydrogen (H2), (4) commonly paramagnetic, (5) stereochemical character nonbonding electron pairs less pronounced, (6) antiferromagnetic coupling unpaired electrons polymetallic prevalent. (25) contrast, generally display opposite characteristics, leading widespread perception inherently vibrant However, discoveries regarding latter part 20th century 21st revealed p block possess properties fundamentally lighter counterparts.Numerous feasibility synthesizing novel more following (Al), silicon (Si), phosphorus (P), possessing open sites, quasi-open frustrated pairs, paramagnetic configurations (i.e., radicals) featuring localized singlet diradicaloid configurations. Researchers recognized behavior undergoes alterations increasing atomic number, aligning Additionally, newly displayed H2 (75,76) C2H4 (77) mild conditions, indicating potential catalytic applications.Substantial highlighted preconceptions incorrect. 2005 digermyne Ar′GeGeAr′ germanium alkyne, Ar′ C6H3-2,6-(C6H3-2,6-iPr2)2) reacts dihydrogen ambient temperature give products Ar′HGeGeHAr′, Ar′H2GeGeH2Ar′, Ar′GeH3. direct unsaturated, closed shell compound conditions. (78) react directly range distannynes (ArSnSnAr, Ar ligand) ca. 25 °C 1 atm pressure afford symmetric bridged stannylene (1b–3b) unsymmetric stannylstannane (4b) high yield 6a). (79) proposed mechanism activated may 6b) interacts LUMO (n+, "virtual lone pairs") HOMO (π) single tin atom complex, producing asymmetric product 4b (with encumbered ligands), then rearranged structure 1b–3b electronically modified ligands).A spectacular possible distannyne ethylene. treatment either AriPr4SnSnAriPr4 [AriPr4 C6H3-2,6(C6H3-2,6-iPr2)2, 1] AriPr8SnSnAriPr8 [AriPr8 C6H-2,6(C6H2-2,4,6-iPr3)2-3,5-iPr2, 2] generates AriPr4Sn(μ2:η1:η1-C2H4)2SnAriPr4 AriPr8Sn(μ2:η1:η1-C2H4)2SnAriPr8 (4). Ethylene incorporation 3 4 involves tin–carbon σ fully reversible hydrocarbon solutions revert 2 elimination reduced standing 7a). 7b) involve synergistic interaction C–C π empty "lone pair" n+ combination Sn–Sn orbital π* level. Subsequent binding second follow rearrangement 4.These findings interest indicated frequency reviews topics cited. Prominent recent highlight include, σ-bond metathesis tin(II) centers (80) carbon–carbon acyclic silylenes, (81) progress continues proceed pace.Dispersion Effect Donor (DED) copied!Attractive intermolecular interactions, bonding, dipoles, London dispersion force, students classroom. Most practicing chemists struggle identify displays hallmarks interactions. substantially weaker strength, attraction discussed outside classroom introduction, effects simply overlooked [although (LDEs) always present molecules].While consistently ions, later counterintuitive features congested intramolecular effects. identified 2013 dichalcogenolate trend decreasing ligand–element–ligand bulk 8). (82) predicted basis considerations alone.Figure 6Figure 6. (a) distannynes. (b) Possible overlaps H2. Figure adapted ref (79).High 7Figure 7. Reversible ArSnSnAr [Ar AriPr4(C6H3-2,6(C6H3-2,6-iPr2)2) AriPr8(C6H-2,6(C6H3-2,4,6-iPr2)2-3,5-iPr2)]. Initial step (77).High 8Figure 8. finding inverse tetrylenes initiated yearslong attractive Adapted (82). Copyright Society.High 9Figure 9. Attractive interligand LDEs critical stability distannene above. Close H–H contacts (here green) cyclohexyl substituents indication (84). 2022 SlidePrior results, 2011 computational investigation Grimme Schreiner hexaphenylethane derivative, (83) phenomenon explaining trends above.These results designed incorporate exploit them. (84) cultural bifurcation continued focus sought scenarios both obvious significant. guided 1970s Bower Tennent (85) Theopold (86) Dimitrov Linden, (87) high-valent norbornyl well aforementioned Schreiner. all cases, unrecognized rigid, hydrocarbon-rich effort required level cooperation collaborators order determine responsible observations Stefan Grimme, Heikki Tuononen, Petra Vasko.The intentional exploitation so-called "Wigley" −N(SiMe3)Dipp (Dipp C6H3-2,6-iPr2). (88) These bisamido M{N(SiMe3)Dipp}2 exhibited rigorously linear geometries short metal–nitrogen bonds. (89) copper, dispersion-effect-induced disproportionation formation Cu(II) Cu{N(SiMe3)Dipp}2. (90) observed (if understood) species, until copper(II) manifestation LDEs.The lab's direction afforded triply bonded imido (91) solution-stable diplumbynes depends presence DED (92) freestanding copper atoms. (93) each stability. Further validation importance Fürstner's 2017 tetra(cyclohexyl)iron(IV) 2-adamantyl analogue. (94) case confer β-hydrogen despite hydrogens underlined rigid cyclic caged enforcing strong LDEs. Inspired this, integrated cyclopentyl design. subtle variations used rise {Sn(PhCy3)2}2 9) equilibrium mixture {Sn(PhCyp3)2}2 cyclotristannane {Sn(PhCyp3)2}3 (PhCy3 −C6H2-2,4,6-Cy3; PhCyp3 −C6H2-2,4,6-Cyp3; Cy cyclohexyl; Cyp cyclopentyl). (95,96)Concluding RemarksClick copied!In closing Editorial, emphasize curiosity driving force behind career, research, inspired co-workers, colleagues "established" science. selection included virtual learned accomplished hope encouraged pursue own curiosity.Author InformationClick copied!Corresponding AuthorCary Stennett, https://orcid.org/0000-0002-2727-5747, Email: [email protected]AuthorsJoshua Queen, https://orcid.org/0000-0002-6726-417XKarin Peng, https://orcid.org/0000-0002-6780-2468Clifton Wagner, https://orcid.org/0000-0002-8045-7777NotesViews expressed necessarily views ACS.ReferencesClick copied! references 96 publications. 1Gynane, M. S.; Hudson, A.; Lappert, F.; Power, Synthesis spin resonance dialkyls diamides arsenic, R12M· (R22N)2M. Soc., Commun. 1976, 16, 623– 624, DOI: 10.1039/C39760000623 Google ScholarThere record reference.2Gynane, Miles, S. J.; Ready halide amide; free-radical pathway. J

Language: Английский

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A mono-coordinated gallium(I) ambiphile with redox-active and redox-inert reactivity

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: April 11, 2024

Mono-coordinated metallyenes (R–M:) of the Group 13 elements feature a non-bonding pair electrons together with two vacant orbitals, which makes them highly reactive ambiphiles that readily activate small molecules by oxidative addition. In consequence their pronounced reactivity, examples mono-coordinated organometallics aluminium(I) and gallium(I) remain rare. Here, we report one-step synthesis monomeric compound undergoes addition reactions and, more remarkably, carbometalation alkynes retention low oxidation state +I coordination number one at gallium. This contrasts previous reports on reactivity low-valent main-group compounds, are regularly oxidized to compounds in stable higher state. These findings provide new approach access pave way for development novel bond-functionalisation strategies hence could enable catalytic processes future.

Language: Английский

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