Organometallics最新文献

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Updates to the Organometallics Team
IF 2.5 3区 化学
Organometallics Pub Date : 2025-02-10 DOI: 10.1021/acs.organomet.5c0001010.1021/acs.organomet.5c00010
Paul J. Chirik, 
{"title":"Updates to the Organometallics Team","authors":"Paul J. Chirik, ","doi":"10.1021/acs.organomet.5c0001010.1021/acs.organomet.5c00010","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00010https://doi.org/10.1021/acs.organomet.5c00010","url":null,"abstract":"","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"457–458 457–458"},"PeriodicalIF":2.5,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Alkyne Carboamination with Imines Catalyzed by [py2TiCl2N(p-tol)]2
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-28 DOI: 10.1021/acs.organomet.4c0049910.1021/acs.organomet.4c00499
Ross F. Koby,  and , Ian A. Tonks*, 
{"title":"Alkyne Carboamination with Imines Catalyzed by [py2TiCl2N(p-tol)]2","authors":"Ross F. Koby,&nbsp; and ,&nbsp;Ian A. Tonks*,&nbsp;","doi":"10.1021/acs.organomet.4c0049910.1021/acs.organomet.4c00499","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00499https://doi.org/10.1021/acs.organomet.4c00499","url":null,"abstract":"<p >α,β-Unsaturated imines are valuable functional groups that lack a general, reliable synthetic route. Here, we report that simple Ti imido halide precatalysts of the type [py<sub>2</sub>TiCl<sub>2</sub>N(Ar)]<sub>2</sub> can catalyze alkyne carboamination with imines, yielding highly substituted α,β-unsaturated imines. [py<sub>2</sub>TiCl<sub>2</sub>N(Ar)]<sub>2</sub> complexes can catalyze an expanded scope of substrates relative to earlier-reported cationic Ti complexes, albeit with modest yields. Several key side products of carboamination have been identified, indicating that low-valent Ti species resulting from catalyst decomposition may be limiting productive catalysis.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"477–482 477–482"},"PeriodicalIF":2.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371945","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
3H-1,2,3,4-Triazaphosphole Constructs Derived from Sterically Encumbered Aryl Polyazides: Synthesis, Structure, and Reactivity
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-24 DOI: 10.1021/acs.organomet.4c0031810.1021/acs.organomet.4c00318
Marimuthu Rajendiran, Martin Papke, Christian Müller* and Ramaswamy Murugavel*, 
{"title":"3H-1,2,3,4-Triazaphosphole Constructs Derived from Sterically Encumbered Aryl Polyazides: Synthesis, Structure, and Reactivity","authors":"Marimuthu Rajendiran,&nbsp;Martin Papke,&nbsp;Christian Müller* and Ramaswamy Murugavel*,&nbsp;","doi":"10.1021/acs.organomet.4c0031810.1021/acs.organomet.4c00318","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00318https://doi.org/10.1021/acs.organomet.4c00318","url":null,"abstract":"<p >Starting from sterically hindered aniline derivatives containing one or more Ar–NH<sub>2</sub> moieties, a series of aryl-azides have been synthesized. The reactions of these mono-, di-, and triaryl azides, ArN<sub>3</sub>, (ArN<sub>3</sub>)<sub>2</sub>, and (ArN<sub>3</sub>)<sub>3</sub> with phosphaalkynes R–C≡P (R = adamantyl or 2,4,6-tri-<i>t</i>-butylphenyl) yielded mono-, bis-, and tris-triazaphosphole assemblies. All the products are formed under ambient conditions under prolonged stirring. Representative triazaphospholes can be selectively alkylated with Meerwein’s reagent on the most nucleophilic nitrogen atom to yield stable 1,2,3,4-triazaphospholenium cations. These compounds were characterized by multinuclear NMR spectroscopy (<sup>1</sup>H, <sup>13</sup>C, <sup>31</sup>P, <sup>19</sup>F, and <sup>11</sup>B), mass spectrometry, and photophysical studies. Molecular structures of representative compounds have also been determined by single crystal X-ray diffraction. Additional density functional theory (DFT), TD-DFT, and NICS calculations were performed and the result were found to be in agreement with our experimental findings.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"502–519 502–519"},"PeriodicalIF":2.5,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Flash Communication: Ligand Centered Cooperative O–H Bond Splitting by a Mo(CO)5(phosphine) Complex
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-22 DOI: 10.1021/acs.organomet.4c0050710.1021/acs.organomet.4c00507
Sotirios Pavlidis,  and , Josh Abbenseth*, 
{"title":"Flash Communication: Ligand Centered Cooperative O–H Bond Splitting by a Mo(CO)5(phosphine) Complex","authors":"Sotirios Pavlidis,&nbsp; and ,&nbsp;Josh Abbenseth*,&nbsp;","doi":"10.1021/acs.organomet.4c0050710.1021/acs.organomet.4c00507","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00507https://doi.org/10.1021/acs.organomet.4c00507","url":null,"abstract":"<p >The synthesis and reactivity of a molybdenum carbonyl complex ligated by geometrically constrained phosphorus trisamide are reported. Reaction with potassium <i>tert</i>-butoxide or methanol triggers ligand-centered substrate activation, leading to planarization of the phosphine donor ligand. P–O bond formation, decarbonylation, and insertion of the molybdenum center into a ligand P–N bond result in the formation of molybdenum tetracarbonyl complexes ligated by rigid N,P-chelate ligands.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"483–486 483–486"},"PeriodicalIF":2.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00507","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Tuning the Terminal N* and C^ Moieties Toward Tailored Pt(II) Complexes with Thiazole-Based N*N^C Luminophores
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-21 DOI: 10.1021/acs.organomet.4c0029810.1021/acs.organomet.4c00298
Stefan Buss, Leon Geerkens, Rose Jordan, Lukas Kletsch, Alexander Hepp, Jutta Kösters, Axel Klein* and Cristian A. Strassert*, 
{"title":"Tuning the Terminal N* and C^ Moieties Toward Tailored Pt(II) Complexes with Thiazole-Based N*N^C Luminophores","authors":"Stefan Buss,&nbsp;Leon Geerkens,&nbsp;Rose Jordan,&nbsp;Lukas Kletsch,&nbsp;Alexander Hepp,&nbsp;Jutta Kösters,&nbsp;Axel Klein* and Cristian A. Strassert*,&nbsp;","doi":"10.1021/acs.organomet.4c0029810.1021/acs.organomet.4c00298","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00298https://doi.org/10.1021/acs.organomet.4c00298","url":null,"abstract":"<p >The synthesis, characterization, cyclovoltammetric and photophysical properties of 11 new <i>d</i><sup>8</sup>-configured Pt(II) complexes with N*N^C coordinated ligands, alternatively involving N*N six-ring and N^C five-ring chelates, are presented. By using various boronic acids, variation of the cyclometalating aryl units was achieved. The DFT-calculated HOMOs are localized on the metal with contributions from the Cl<sup>–</sup> coligand and either the phenyl/thiophenyl unit or the thiazolyl moiety, depending on the substitution pattern. The LUMOs have phenyl-pyridine π*-character. Both calculated orbital sets agree well with the redox potentials from cyclic voltammetry. The TD-DFT calculated absorption spectra are in agreement with experimental data showing long-wavelength bands in the range from 400 to 500 nm, which matches the yellow color of the complexes. The ligand variation enabled a fine-tuning of the emissive properties related to the resulting complexes, going from greenish-blue (471 nm) to red (617 nm) phosphorescence. The position of the substituent affects the excited state properties, which is attributed to mesomeric and inductive effects on the Pt–C bond and the adjacent pyridine ring. In general, modulation of the excited state character can be achieved by variation of the cyclometalating unit, thus affecting the excited state energy as well as the radiative and radiationless deactivation rates.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"487–501 487–501"},"PeriodicalIF":2.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Intramolecular Oxidative Addition Triggered by One-Electron Oxidation of Molybdenum(iii) Tris(anilide): Generation of Molybdenum(v) Imido Aryl Bis(anilide) by Autocatalysis
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-21 DOI: 10.1021/acs.organomet.3c0050210.1021/acs.organomet.3c00502
Albert Paparo*, Tobias Schindler, Jan van Leusen, Jessica Cook, Thomas P. Spaniol, Paul Kögerler, Manuel Temprado*, Christopher C. Cummins* and Jun Okuda*, 
{"title":"Intramolecular Oxidative Addition Triggered by One-Electron Oxidation of Molybdenum(iii) Tris(anilide): Generation of Molybdenum(v) Imido Aryl Bis(anilide) by Autocatalysis","authors":"Albert Paparo*,&nbsp;Tobias Schindler,&nbsp;Jan van Leusen,&nbsp;Jessica Cook,&nbsp;Thomas P. Spaniol,&nbsp;Paul Kögerler,&nbsp;Manuel Temprado*,&nbsp;Christopher C. Cummins* and Jun Okuda*,&nbsp;","doi":"10.1021/acs.organomet.3c0050210.1021/acs.organomet.3c00502","DOIUrl":"https://doi.org/10.1021/acs.organomet.3c00502https://doi.org/10.1021/acs.organomet.3c00502","url":null,"abstract":"<p >One-electron oxidation of molybdenum(<span>iii</span>) tris(anilide) Mo(N[<sup><i>t</i></sup>Bu]Ar)<sub>3</sub> (Ar: Ar<sup>Me</sup> = 3,5-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub> and Ar<sup>Ph</sup> = 3,5-Ph<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) led to intramolecular oxidative addition across the N–C<sub>ipso</sub> bond of a ligated anilide to form the cationic Mo(<span>vi</span>) imido/aryl bis(anilide) complexes [Mo(N[<sup><i>t</i></sup>Bu]Ar)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar)][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]. One-electron reduction of [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] allowed access to the neutral Mo(v) species [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)]. The d<sup>1</sup> electron configuration was confirmed through EPR spectroscopy and the Evans method. Compound [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)] was experimentally and theoretically shown to be stable against reductive elimination which would form the energetically less favorable Mo(N[<sup><i>t</i></sup>Bu]Ar)<sub>3</sub>. The high activation barrier has so far prevented Mo(N[<sup><i>t</i></sup>Bu]Ar)<sub>3</sub> from isomerizing spontaneously to [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)]. An autocatalytic process was developed to access [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)] through reduction of [Mo(N[<sup><i>t</i></sup>Bu]Ar<sup>Me</sup>)<sub>2</sub>(═N<sup><i>t</i></sup>Bu)(Ar<sup>Me</sup>)][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] by Mo(N[<sup><i>t</i></sup>Bu]Ar)<sub>3</sub>, which itself was converted into the oxidizing agent. Attempts to access stable Mo(<span>iv</span>) cations with 4,4′-bipyridine only resulted in labile binding of 4,4′-bipyridine to one or two molybdenum(<span>iii</span>) tris(anilide) complexes.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"529–535 529–535"},"PeriodicalIF":2.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Flash Communication: Rearrangement of a tris-Carbene Ligand Precursor to an all-N-Bound tris-Imidazole Iron Complex: Flipping the Umbrella
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-21 DOI: 10.1021/acs.organomet.4c0044510.1021/acs.organomet.4c00445
Tom Hartmann, Lisa Pick, Frank W. Heinemann, Andreas Scheurer and Karsten Meyer*, 
{"title":"Flash Communication: Rearrangement of a tris-Carbene Ligand Precursor to an all-N-Bound tris-Imidazole Iron Complex: Flipping the Umbrella","authors":"Tom Hartmann,&nbsp;Lisa Pick,&nbsp;Frank W. Heinemann,&nbsp;Andreas Scheurer and Karsten Meyer*,&nbsp;","doi":"10.1021/acs.organomet.4c0044510.1021/acs.organomet.4c00445","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00445https://doi.org/10.1021/acs.organomet.4c00445","url":null,"abstract":"<p >Treatment of the ligand precursor H<sub>3</sub>TIMMN<sup>Mes</sup>Cl<sub>3</sub> (TIMMN<sup>Mes</sup> = <i><b>t</b>ris</i>-[(3-mesityl-<b>im</b>idazol-2-ylidene)<b>m</b>ethyl]ami<b>n</b>e) with an excess of base yields the literature-known ferrous <i>tris</i>-<i>N</i>-heterocyclic carbene (NHC) complex [(TIMMN<sup>Mes</sup>)Fe<sup>II</sup>Cl]Cl (<b>1-Cl</b>). In contrast, utilizing a substoichiometric amount of base initiates a unique rearrangement of all three NHC pendant arms to yield the tripodal, all-<i>N</i>-bound <i>tris</i>-imidazole [(<i>N</i>-TIMMN<sup>Mes</sup>)Fe<sup>II</sup>Cl]Cl (<b>2-Cl</b><sub><b>sol</b></sub>). Divalent <b>2-Cl</b> and <b>2-PF</b><sub><b>6</b></sub> are fully characterized, structurally by single-crystal X-ray diffraction analysis and spectroscopically by <sup>1</sup>H NMR and <sup>57</sup>Fe Mössbauer spectroscopy as well as SQUID magnetization measurements, to demonstrate the influence of the change from a soft strong-field to a hard weak-field ligand. Optimized reaction conditions for the reproducible, high-yield carbene-to-imidazole rearrangement were developed in a series of experiments.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"464–467 464–467"},"PeriodicalIF":2.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Molecular Insight into Hydrodeoxygenation of Naphthols: Iridium-Catalyzed Ring Hydrogenation and Substrate-Catalyzed Dehydration
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-20 DOI: 10.1021/acs.organomet.4c0046210.1021/acs.organomet.4c00462
Christian Sant Gjermestad, Shuhei Kusumoto, Iván Flores-Linares, Giovanni Occhipinti, Erwan Le Roux, Hideaki Ando, Kyoko Nozaki* and Vidar R. Jensen*, 
{"title":"Molecular Insight into Hydrodeoxygenation of Naphthols: Iridium-Catalyzed Ring Hydrogenation and Substrate-Catalyzed Dehydration","authors":"Christian Sant Gjermestad,&nbsp;Shuhei Kusumoto,&nbsp;Iván Flores-Linares,&nbsp;Giovanni Occhipinti,&nbsp;Erwan Le Roux,&nbsp;Hideaki Ando,&nbsp;Kyoko Nozaki* and Vidar R. Jensen*,&nbsp;","doi":"10.1021/acs.organomet.4c0046210.1021/acs.organomet.4c00462","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00462https://doi.org/10.1021/acs.organomet.4c00462","url":null,"abstract":"<p >The only molecular precatalysts offering high aromatic selectivity in hydrodeoxygenation (HDO) of phenolic and methyl ether lignin model compounds are hydroxy-tetraphenyl-cyclopentadienyl (CpOH) iridium complexes such as IrCpOH(H)<sub>2</sub>PPh<sub>3</sub> (<b>Ir1</b>) [Kusumoto, S.; Nozaki, K. <i>Nat. Commun.</i> <b>2015</b>, 6, 6296]. Here, we synthesized a variant (<b>Ir1L</b>) in which the CpOH and phosphine moieties are tethered and unlikely to dissociate from iridium. Surprisingly, unlike <b>Ir1</b>, <b>Ir1L</b> neither catalyzes HDO of phenylphenols nor the interconversion between naphthalene and tetralin. The density functional theory-calculated barriers for the corresponding reactions catalyzed by unmodified <b>Ir1</b> or <b>Ir1L</b> are high (&gt;44 kcal/mol), suggesting that the observed activity of <b>Ir1</b> in these reactions is due to catalyst initiation. In contrast, intact <b>Ir1</b> and <b>Ir1L</b> both appear to catalyze HDO of naphthols. Notably, the calculations show that <b>Ir1</b> and <b>Ir1L</b> both mediate initial ring hydrogenation to 1,2-dihydronaphthol (<b>2H</b>), while only <b>Ir1L</b> can continue hydrogenation to 1,2,3,4-tetrahydronaphthol (<b>4H</b>). The subsequent substrate-catalyzed dehydration of <b>2H</b> leads directly to naphthalene, whereas that of <b>4H</b> leads to 1,2-dihydronaphthalene and, via hydrogenation, to tetralin. The calculations are thus consistent with the near-perfect aromatic selectivity observed at short reaction times using <b>Ir1</b> and the mixture (19:81) of naphthalene and tetralin obtained by using <b>Ir1L</b>.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"536–546 536–546"},"PeriodicalIF":2.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00462","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis and Reactivity of a Paramagnetic Iron Phosphaethynolate Complex
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-18 DOI: 10.1021/acs.organomet.4c0044710.1021/acs.organomet.4c00447
Duleeka C. Wannipurage, Austin D. Chivington, Yaroslav Losovyj, Maren Pink and Jeremy M. Smith*, 
{"title":"Synthesis and Reactivity of a Paramagnetic Iron Phosphaethynolate Complex","authors":"Duleeka C. Wannipurage,&nbsp;Austin D. Chivington,&nbsp;Yaroslav Losovyj,&nbsp;Maren Pink and Jeremy M. Smith*,&nbsp;","doi":"10.1021/acs.organomet.4c0044710.1021/acs.organomet.4c00447","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00447https://doi.org/10.1021/acs.organomet.4c00447","url":null,"abstract":"<p >The bulky iron(II) tris(carbene)borate complex PhB(AdIm)<sub>3</sub>FeCl reacts with equimolar NaPCO to afford PhB(AdIm)<sub>3</sub>Fe(PCO) as a rare example of a paramagnetic phosphaethynolate complex. Although thermally and photochemically unstable, there is no evidence that either of these conditions leads to the formation of an iron phosphido complex. However, in the presence of excess NaPCO, thermolysis of PhB(AdIm)<sub>3</sub>Fe(PCO) yields a dinuclear iron complex in which a new side-bound diphosphene ligand is stabilized by <i>N</i>-heterocyclic carbene and borate groups. These results hint at the utility of paramagnetic complexes for enlarging the scope of phosphaethynolate chemistry.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"468–471 468–471"},"PeriodicalIF":2.5,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation
IF 2.5 3区 化学
Organometallics Pub Date : 2025-01-17 DOI: 10.1021/acs.organomet.4c0045410.1021/acs.organomet.4c00454
Jewelianna M. Moore, Yun Ji Park and Alison R. Fout*, 
{"title":"Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation","authors":"Jewelianna M. Moore,&nbsp;Yun Ji Park and Alison R. Fout*,&nbsp;","doi":"10.1021/acs.organomet.4c0045410.1021/acs.organomet.4c00454","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00454https://doi.org/10.1021/acs.organomet.4c00454","url":null,"abstract":"<p >High-valent iron complexes play a crucial role in the oxidation of organic substrates, especially in C–H bond functionalization reactions in biology. This paper investigates the reactivity of nonporphyrin tripodal ligands featuring a secondary coordination sphere, focusing on their prospective ability to stabilize high-valent iron-oxo species. Using NMR spectroscopy and X-ray crystallography, we detail the formation of an Fe(III)-alkoxide complex through intramolecular C–H bond activation, providing insight into the potential transient formation of a high-valent iron-oxo intermediate. While attempts to observe an Fe(IV)-oxo complex were unsuccessful, our findings underscore the significance of the ligand electronic environment in stabilizing reactive iron species for C–H bond activation.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 3","pages":"472–476 472–476"},"PeriodicalIF":2.5,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00454","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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