Organometallics最新文献

Titanium Carboxylate Complexes through CO2 Capture

IF 2.5 3区化学

Organometallics Pub Date : 2025-04-02 DOI: 10.1021/acs.organomet.5c0002310.1021/acs.organomet.5c00023

Marcel Eilers, Kevin Schwitalla, Marc Schmidtmann and Rüdiger Beckhaus*,

{"title":"Titanium Carboxylate Complexes through CO2 Capture","authors":"Marcel Eilers, Kevin Schwitalla, Marc Schmidtmann and Rüdiger Beckhaus*, ","doi":"10.1021/acs.organomet.5c0002310.1021/acs.organomet.5c00023","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00023https://doi.org/10.1021/acs.organomet.5c00023","url":null,"abstract":"Addition of gaseous CO2 to solutions of bis(π-η5:σ-η1-pentafulvene)titanium complexes results in the selective insertion reaction of one equivalent of O═C═O into one of the two frustrated Ti–Cexo bonds under mild conditions. The formation of κ1O- and κ2O,O-carboxylate titanium complexes is observed and characterized by single crystal X-ray analysis, NMR and IR spectroscopy. The nature of Ti–O interactions is established by computational studies. The reactivity of the remaining pentafulvene ligand is demonstrated in reactions with H-acidic and multiple-bond-containing substrates. The reactions with etheric HCl results in the selective formation of Ti–Cl complexes by protonation of the second pentafulvene moiety, disregarding the carboxylate ligand. The formed chlorido complexes are used in follow-up reactions with methyllithium, resulting in the methylation of the complexes via salt metathesis reactions, and reduction of the chloride complexes with sodium amalgam results in the formation of dimeric κ1O-μ-O/bridged-carboxylate Ti(III) complexes.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"866–874 866–874"},"PeriodicalIF":2.5,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.5c00023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825267","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

Nickel Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-29 DOI: 10.1021/acs.organomet.5c0003310.1021/acs.organomet.5c00033

Maximilian Roca Jungfer, Frank Rominger, Thomas Oeser, A. Stephen K. Hashmi and Thomas Schaub*,

{"title":"Nickel Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands","authors":"Maximilian Roca Jungfer, Frank Rominger, Thomas Oeser, A. Stephen K. Hashmi and Thomas Schaub*, ","doi":"10.1021/acs.organomet.5c0003310.1021/acs.organomet.5c00033","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00033https://doi.org/10.1021/acs.organomet.5c00033","url":null,"abstract":"In a study to expand the coordination chemistry of methylene-extended 4,5-bis(diorganophosphinomethyl)acridine ligands (LR) to first-row transition metal ions, bidentate P,P-chelated nickel complexes of these usually tridentate pincer ligands were identified. Similar to the iron complexes of these ligands, the acridines’ nitrogen atom does not coordinate to nickel, leading to the formation of nickel bisphosphine-type complexes adopting both cis- and trans-coordination modes. Nickel complexes with compositions [NiX2(κ2-LR)] (X = Cl, Br, I, CO, CN, and R = Cy, iPr) were isolated and characterized. The bisphosphine ligands are weakly bound to nickel and can be transferred from [NiCl2(κ2-LR)] to [ClAu(SMe2)], giving the gold(I) cations [Au(LR)]+. The chlorido ligands are selectively exchanged for CN– during the reaction of [NiCl2(κ2-LR)] with KCN, giving trans-[Ni(CN)2(κ2-LCy)]. In contrast, the nickel(0) carbonyls [Ni(CO)2(κ2-LR)] form in photochemical reactions from [Ni(CO)2(PPh3)2] and LR in partially reversible reactions and are intrinsically unstable in solution.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"882–891 882–891"},"PeriodicalIF":2.5,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825296","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

Arene Insertion into the M–Cl Bond vs Addition-like Behavior of Arene and M–Cl Bond (M = Cu/Fe): A DFT Investigation of the Cu/Fe SET Mechanism of Arene sp2 C–H Chlorination

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-27 DOI: 10.1021/acs.organomet.4c0048910.1021/acs.organomet.4c00489

Wei Xu*, Peili Li and Yin Huang*,

引用次数: 0

Site-Selectivity of C(sp2)–H Oxidative Addition of Fluorinated Arenes with Pyridine(dicarbene) Cobalt(I) Complexes and Aryl Isomerization

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-26 DOI: 10.1021/acs.organomet.4c0045210.1021/acs.organomet.4c00452

Haozheng Li, Hanna H. Cramer, Jose B. Roque and Paul J. Chirik*,

{"title":"Site-Selectivity of C(sp2)–H Oxidative Addition of Fluorinated Arenes with Pyridine(dicarbene) Cobalt(I) Complexes and Aryl Isomerization","authors":"Haozheng Li, Hanna H. Cramer, Jose B. Roque and Paul J. Chirik*, ","doi":"10.1021/acs.organomet.4c0045210.1021/acs.organomet.4c00452","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00452https://doi.org/10.1021/acs.organomet.4c00452","url":null,"abstract":"The rate, site-selectivity, and product isomerization of the C(sp2)–H oxidative addition of arenes with pyridine(dicarbene) cobalt methyl and phenyl complexes have been investigated with four representative arenes of varying electronic and steric properties. The rates of C(sp2)–H activation to yield cobalt-aryl products and subsequent aryl isomerization were influenced by the electronic properties of the arene; the relatively electron-poor arene 3-fluorobenzotrifluoride underwent C(sp2)–H activation and isomerization of the cobalt-aryl more than 70 times faster than the more electron-rich substrate, 3-fluoro-N,N,α-trimethylbenzeneacetamide. In all cases, meta-to-fluorine C(sp2)–H oxidative addition was the major product at low conversion, which subsequently isomerized to the ortho isomer over time. Deuterium-labeling experiments and measurement of methane isotopologues establish that the major cobalt-aryl product at early conversion arises from kinetically preferred, meta-selective oxidative addition. Density functional theory calculations support pathways involving cobalt(I)–(III) redox cycles with oxidative addition to cobalt(I) occurring with a relatively high barrier followed by faster reductive elimination. Despite the strong σ-donating properties of the pyridine(dicarbene) pincer ligand, the π-accepting character of the carbene donors lowers the barrier for reductive elimination, and hence, cobalt(III) intermediates have not been observed.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"807–815 807–815"},"PeriodicalIF":2.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825062","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

Pt(II), Pd(II), and Ni(II) Complexes with Tridentate Cyclometalating Five- and Six-Ring Chelating N^C*N, C^N*N, and N*C*N Quinolinyl Ligands

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-26 DOI: 10.1021/acs.organomet.4c0050010.1021/acs.organomet.4c00500

Leo Payen, Tobias Lapić, Mathias Wickleder and Axel Klein*,

{"title":"Pt(II), Pd(II), and Ni(II) Complexes with Tridentate Cyclometalating Five- and Six-Ring Chelating N^C*N, C^N*N, and N*C*N Quinolinyl Ligands","authors":"Leo Payen, Tobias Lapić, Mathias Wickleder and Axel Klein*, ","doi":"10.1021/acs.organomet.4c0050010.1021/acs.organomet.4c00500","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00500https://doi.org/10.1021/acs.organomet.4c00500","url":null,"abstract":"Nine cyclometalated Ni(II), Pd(II), and Pt(II) complexes of the type [M(NCN)Cl] and [M(CNN)X] (X = Cl for Pt and Pd, or Br for Ni) containing 8-quinolinyl (Q), 2-pyridyl (Py), and phenyl (Ph) moieties are presented. The introduction of Q leads to six-ring chelates (N*C or N*N) compared with five-ring chelates (C^N or N^N) for 2-pyridyl-containing systems in the PyPhQ– (N^C*N), QPhQ– (N*C*N), and PhPyQ– (C^N*N) ligands. Single-crystal X-ray diffractometry showed the six-ring chelate units with angles around 90° compared with 80° for the five-ring chelates. Marked tilts of the planar Q systems toward the central Py or Ph core (up to 37°) were observed. Cyclic voltammetry showed first reduction potentials varying from −1.8 to −2.2 V vs ferrocene/ferrocenium and oxidations at around 0.45 V for Pt, 0.75 V for Pd, and 0 V for Ni complexes. DFT-calculated energies and compositions of the frontier molecular orbitals allowed assigning reductions to ligand-centered processes and oxidations to processes with mixed X(p)/M(d)/Ph(π) contributions. Long-wavelength UV–vis absorption maxima ranging from 400 to 430 nm were assigned to mixed ligand-centered(π–π*)/metal(d)-to-ligand(π*) transitions. The new complex [Pt(PyPhQ)Cl] showed very long-wavelength photoluminescence (>600 nm), similar to that of the previously reported [Pt(QPhQ)Cl] derivative.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"847–857 847–857"},"PeriodicalIF":2.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825300","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

Attempts toward a Silyl-Stabilized Dicoordinate Borylene: Insertion of Carbon Dioxide into the B–Si Bond

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-26 DOI: 10.1021/acs.organomet.5c0005010.1021/acs.organomet.5c00050

Kasperi M. Salonen, J. Mikko Rautiainen, Aaron Mailman, Chris Gendy and Heikki M. Tuononen*,

{"title":"Attempts toward a Silyl-Stabilized Dicoordinate Borylene: Insertion of Carbon Dioxide into the B–Si Bond","authors":"Kasperi M. Salonen, J. Mikko Rautiainen, Aaron Mailman, Chris Gendy and Heikki M. Tuononen*, ","doi":"10.1021/acs.organomet.5c0005010.1021/acs.organomet.5c00050","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00050https://doi.org/10.1021/acs.organomet.5c00050","url":null,"abstract":"One-electron reduction of the carbene-stabilized borane (Me2-cAAC)B(Cl)2Si(SiMe3)3, 1, with potassium naphthalenide gave the radical (Me2-cAAC)B(Cl)Si(SiMe3)3, 2. A subsequent one-electron reduction of 2 yielded the dicoordinate borylene (Me2-cAAC)BSi(SiMe3)3, 3, which rapidly underwent intramolecular C–H activation to give cyclo-(Me2-cAAC)B(H)Si(SiMe3)3, 4, irrespective of the employed reaction conditions. Compound 3 could be stabilized as the carbonyl complex (Me2-cAAC)B(CO)Si(SiMe3)3, 5, that gave 4 upon irradiation with a UV light under a CO2 atmosphere. In contrast, the two-electron reduction of 1 under an atmosphere of CO2 yielded a mixture of products of which (Me2-cAAC)B(Cl)(H)C(O)OSi(SiMe3)3, 6, could be separated and structurally characterized. Compound 6 is a rare example of CO2 insertion into a B–E (E = heavier main group element) bond in which boron functions as a nucleophile, thereby mimicking transition metal-mediated carboxylation. The mechanism for the formation of 6 from the purported boryl anion intermediate [(Me2-cAAC)B(Cl)Si(SiMe3)3]−, 2–, was analyzed computationally.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"899–904 899–904"},"PeriodicalIF":2.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825061","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

Host–Guest Complexes of Cyclopentadienyl Iron Dicarbonyl (CpFe(CO)2) CO-Releasing Molecules with Cucurbit[7]uril

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-25 DOI: 10.1021/acs.organomet.4c0046910.1021/acs.organomet.4c00469

Rodrigo P. Monteiro, Isabel B. Calhau, Ana C. Gomes, Ricardo F. Mendes, Filipe A. Almeida Paz, André D. Lopes, José P. Da Silva, Carlos C. Romão, Isabel S. Gonçalves and Martyn Pillinger*,

{"title":"Host–Guest Complexes of Cyclopentadienyl Iron Dicarbonyl (CpFe(CO)2) CO-Releasing Molecules with Cucurbit[7]uril","authors":"Rodrigo P. Monteiro, Isabel B. Calhau, Ana C. Gomes, Ricardo F. Mendes, Filipe A. Almeida Paz, André D. Lopes, José P. Da Silva, Carlos C. Romão, Isabel S. Gonçalves and Martyn Pillinger*, ","doi":"10.1021/acs.organomet.4c0046910.1021/acs.organomet.4c00469","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00469https://doi.org/10.1021/acs.organomet.4c00469","url":null,"abstract":"Iron(II) cyclopentadienyl carbonyl complexes are promising as CO-releasing molecules (CORMs) for therapeutic applications. In common with other metallodrugs, the practical application of Fe-CORMs may require their conjugation with biocompatible carriers to improve their bioavailability and protect them from premature degradation. Here, we show that the CO-releasing properties of the complexes [CpFe(CO)2Cl] (1) and [CpFe(CO)2CH2CONH2] (2) are retained when noncovalently encapsulated within cucurbit[7]uril (CB7), a well-established drug-enhancing excipient. The inclusion compounds were characterized in the solid-state by single-crystal and powder XRD, ATR-IR spectroscopy, Raman spectroscopy, TGA, and 13C{1H} CP MAS NMR. In the crystal structure of 2@CB7, there are two crystallographically independent [2@CB7] binary complexes that differ in the orientation of the guest molecules inside the CB cavity. High-resolution ESI-MS and 1H NMR studies verified the formation and stability of 1:1 2@CB7 inclusion complexes in an aqueous solution. In a physiological buffer, complex 2 is stable in the dark, but releases ca. 1.4 equiv of CO when irradiated with low-power cold white light, with a half-life (t1/2) of 19.2 ± 1.9 min. The photodecarbonylation behavior of the complexes is largely maintained in the inclusion compounds, with t1/2 of 10.0 ± 0.6 and 21.1 ± 1.9 min for encapsulated 1 and 2.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"824–839 824–839"},"PeriodicalIF":2.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825310","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

Synthesis and Properties of a Cyclopentadienone Tantalum(I) Complex: Large Electron Donation from Ta(I) to the Cyclopentadienone Ligand

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-25 DOI: 10.1021/acs.organomet.5c0000610.1021/acs.organomet.5c00006

Takaya Kondo, Takuya Higashi, Shuhei Kusumoto* and Kyoko Nozaki,

引用次数: 0

Comparative Study of the Structures and Reactivities of Cationic Nickel and Palladium Complexes with a Bismuth-Bisphosphine (PBiP) Ligand

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-21 DOI: 10.1021/acs.organomet.4c0046110.1021/acs.organomet.4c00461

Kim Gates, Yuka Aoyama, Hang Cao and Gongfang Hu*,

{"title":"Comparative Study of the Structures and Reactivities of Cationic Nickel and Palladium Complexes with a Bismuth-Bisphosphine (PBiP) Ligand","authors":"Kim Gates, Yuka Aoyama, Hang Cao and Gongfang Hu*, ","doi":"10.1021/acs.organomet.4c0046110.1021/acs.organomet.4c00461","DOIUrl":"https://doi.org/10.1021/acs.organomet.4c00461https://doi.org/10.1021/acs.organomet.4c00461","url":null,"abstract":"We report the synthesis, structural characterization, and reactivity of a new series of cationic nickel and palladium complexes featuring a bismuth-bisphosphine (PBiP) ligand. By converting neutral R2Bi–transition metal precursors into cationic species, we enhanced Bi–transition metal bond polarization, thereby enabling unique interactions between bismuth and the transition metal centers. Cationic BiPdAcN was synthesized via chloride abstraction from BiPdCl, yielding a species in which the Bi–Pd bond is best described as a Pd(0) → Bi(III) donor–acceptor interaction based on natural bond orbital (NBO) analyses. This interaction exerts a trans influence, as evidenced by the elongation of the Pd–acetonitrile bond. In contrast, the corresponding BiNi complexes, prepared in a single-step synthesis of BiNiCl followed by transformation into BiNiAcN and BiNi2AcN, exhibit a more covalent Bi–Ni bond with minimal trans influence from bismuth. Structural analyses, including X-ray diffraction and NMR spectroscopy, reveal differences in coordination geometries and bond metrics between the Ni and Pd systems. Orbital analysis further substantiates that while the Bi–Pd interaction in the cationic species is highly polarized toward Pd, the Bi–Ni bond is more evenly distributed.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"816–823 816–823"},"PeriodicalIF":2.5,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00461","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825177","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

Magnesium–Ligand Cooperation in Breaking the O–H and C–H Bonds of Water and Diazoalkane

IF 2.5 3区化学

Organometallics Pub Date : 2025-03-20 DOI: 10.1021/acs.organomet.5c0003110.1021/acs.organomet.5c00031

Vishal Sharma, Soumya Ranjan Dash, Kumar Vanka, Rajesh G. Gonnade and Sakya S. Sen*,

{"title":"Magnesium–Ligand Cooperation in Breaking the O–H and C–H Bonds of Water and Diazoalkane","authors":"Vishal Sharma, Soumya Ranjan Dash, Kumar Vanka, Rajesh G. Gonnade and Sakya S. Sen*, ","doi":"10.1021/acs.organomet.5c0003110.1021/acs.organomet.5c00031","DOIUrl":"https://doi.org/10.1021/acs.organomet.5c00031https://doi.org/10.1021/acs.organomet.5c00031","url":null,"abstract":"In our previous paper, we reported that the reaction of a tridentate nacnac ligand with a pendant picolyl group, with KHMDS and MgI2, resulted in the formation of a homoleptic hexacoordinate magnesium compound. Here, we show that the analogous reaction of the ligand with CH3MgBr led to a heteroleptic magnesium bromide species (1). Attempts to generate the magnesium hydride species from 1 led to the dearomatization of the pyridine ring, and the resulting product was a magnesium hydroxide (3) presumably generated due to an adventitious amount of water. The reaction of the ligand with nBu2Mg afforded a unique dearomatized magnesium species (2) in high yield. Theoretical calculations reveal the presence of a nonbonding orbital on the magnesium, susceptible to nucleophilic attack. Indeed, the reaction of 2 with H2O/D2O cleaves the O–H/D bond via magnesium–ligand cooperation and generates a magnesium hydroxide (4 and 5). In addition, 2 reacts with Me3SiCHN2 and cleaves the C–H bond to generate another unusual, well-defined magnesium compound with a bridging isocyanide moiety (6) via migration of the SiMe3 group from the carbon to the nitrogen atom. The latter can be described as a dimer of magnesium isocyanamide. DFT calculations were performed to understand the electronic structures of the synthesized molecules.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 7","pages":"875–881 875–881"},"PeriodicalIF":2.5,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825043","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