Inorganic Chemistry最新文献

{"title":"Nucleophilicity of the Nitrile N Atom Whose Lone Pair Is Blocked by Metal Coordination. The π-Hole Interaction between an Arene Carbon and the Metal-Bound Nitrile Nitrogen","authors":"Yulia N. Toikka, Anton V. Rozhkov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. Bokach","doi":"10.1021/acs.inorgchem.4c03995","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03995","url":null,"abstract":"Cocrystallization of CuI with NCNMe₂ in the presence of substituted perfluoroarenes─iodoperfluorobenzene (IFB), 4,4′-diiodoperfluorobiphenyl (4,4′-FIBP), and 4-bromoperfluorobenzonitrile (4-BrFBN)─led to the formation of three types of adducts <b>1</b>·2(IFB), <b>1</b>·4,4’FIBP, and <b>1</b>·4-BrFBN (<b>1</b> is Cu₄I₄(NCNMe₂)₄), all studied by X-ray crystallography. In these cocrystals, the coordinated nitrile N atom (whose electron pair is engaged in metal coordination) still acts as an electron donor, forming π-hole interactions, specifically, π-hole_arene···N_nitrile, with the perfluoroarenes. These interactions were examined in the context of their occurrence alongside other interactions involving C atoms of the electron-deficient aromatic rings and nucleophilic atoms of the copper cluster. Comprehensive theoretical calculations, including MEP, QTAIM/NCI plot analysis, EDA, ELF projections, and ETS-NOCV calculations, revealed that the nitrile ligand N atom maintains significant negative potential and that π-hole interactions are energetically more favorable than σ-hole interactions in the studied systems. This nucleophilicity is based on a noticeable contribution of the heterocumulene form, Cu–N^–═C═N⁺Me₂, in the resonance hybrid of Cu-bound NCNMe₂: a phenomenon influenced by both the coordination and the conjugation between the NR₂ and CN groups The discovery of π-hole_arene···N_nitrile contacts adds a new dimension to our understanding of coordinated push–pull nitriles, in particular dialkylcyanamides, revealing that the coordinated nitrile N atom can still function as a nucleophile in noncovalent binding.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Supramolecular Assembly, Solvent-Induced, and Mechanochromic Luminescence of Au(I) Quinoline-8-thiolates","authors":"Biing-Chiau Tzeng, Yu-Ting Chen, Jia-Hen Chang, Bing-Jian Sun, Agnes H. H. Chang, Su-Ying Chien","doi":"10.1021/acs.inorgchem.4c03328","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03328","url":null,"abstract":"AuCl(PMe₃) and AuCl(PEt₃) were used to react with quinoline-8-thiolate (8-QNS) to give three Au(I) complexes, i.e., [8-QNS(AuPMe₃)₂]ClO₄ (<b>1</b>), [(8-QNS)₂Ag(AuPMe₃)₂]ClO₄ (<b>2</b>), and [8-QNS(AuPEt₃)₂]ClO₄ (<b>3</b>), which have been structurally determined by X-ray diffraction to show various intra- and intermolecular metal···metal contacts (i.e., metal = Au(I) or Ag(I)). All complexes displayed solid-state luminescence at 535–568 nm, which is most likely attributed to an intraligand transition of 8-QNS and/or a S → Au(I) charge-transfer transition, possibly modified by Au(I)···Au(I) interactions. Notably, complex <b>1</b>·CH₂Cl₂ exhibited remarkable mechanochromic luminescence from 535 to 601 nm upon grinding. While immersed in various solvents for the ground powder samples of complex <b>1</b>·CH₂Cl₂, the luminescence at 601 nm mostly reverted to the original luminescence. Powder X-ray diffraction measurements indicated that complex <b>1</b>·CH₂Cl₂ underwent structural transformation from a crystalline to an amorphous phase upon grinding, and it can be restored to the original crystalline phase upon immersion in various solvents. Additionally, the reversible experiments of complex <b>1</b>·CH₂Cl₂ for the grinding and immersion actions were performed for up to five cycles. Moreover, the time-dependent luminescence spectra for the crystalline samples of complex <b>1</b>·CH₂Cl₂ were measured, and they showed a significant luminescence change from 535 to 590 nm within 2 days.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insertion Behavior of Dialkylgermylene Ge(FluTMS)2 in Different E–X σ Bonds (E = Au, Si, Ge, Sn) and Its Relevance for Germanium Cluster Formation","authors":"Sabrina Jeltsch, Jannik Schulz, Claudio Schrenk, Andreas Schnepf","doi":"10.1021/acs.inorgchem.4c04099","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04099","url":null,"abstract":"We present the insertion behavior of the alkyl-substituted germylene Ge(Flu^TMS)₂ in different E–X σ bonds (E = Au, Si, Ge, Sn), first with the isolation of the germylgold complex (Flu^TMS)₂Ge(Cl)AuPPh₃. Afterward, the oxidative addition of GeCl₄ to Ge(Flu^TMS)₂ gives the digermane (Flu^TMS)₂Ge(Cl)GeCl₃, followed by a reductive elimination of GeCl₂ and the formation of the oxidation product (Flu^TMS)₂GeCl₂. A comparable behavior is observed, with the homologues ECl₄ (E = Si, Sn) stopping at different steps of the reaction. The formation of the germylgermylene (Flu^TMS)₂Ge(Cl)GeCl starting from Ge(Flu^TMS)₂ and GeCl₂·dioxane is also spectroscopically observable, followed by ligand rearrangements to the tetramer [Flu^TMSGeCl]₄. Adding a phosphine as the Lewis base has a direct influence on the stability and structure of (Flu^TMS)₂Ge(Cl)GeCl, leading to the formation of Flu^TMSGeCl·PEt₃ as a stable product. Subsequent investigations of Ge(Flu^TMS)₂ with a metastable Ge(I)Br solution show that at a ratio of 6:1 GeBr/Ge(Flu^TMS)₂ the alkyl-substituted germylene no longer acts as a redox-active agent but as a cluster building block. This link and the involvement of a germylene in insertion reactions give an indication of how the construction or expansion of Ge cluster species can operate.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"51 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sintering Evolving Mn2O3–LaMnO3 Perovskite Heterointerfaces as Highly Active and Durable Catalysts for Catalytic Removal of Volatile Organic Compounds","authors":"Chi Zhang, Jinyan Xiao, Jiajian Gao, Xuan Pang, Lei Yang, Shengwei Tang, Yunfa Chen, Wenxiang Tang","doi":"10.1021/acs.inorgchem.4c04514","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04514","url":null,"abstract":"Improving the catalyst performance for the thermal oxidation reaction faces the daunting challenge of the activity–stability trade-off. Herein, an evolved heterointerface was constructed on spherical Mn₂O₃ nanocatalysts to achieve exceptional stability while maintaining adequate activity by simply introducing La. The generation of the active Mn₃O₄–Mn₂O₃ heterointerfaces by La doping was experimentally observed, which further segregates to the surface during thermal aging and forms epitaxially grown heterostructured LaMnO₃–Mn₂O₃ with Mn atoms. The former can act as highly active sites for the deep oxidation of VOCs due to the richness in oxygen vacancies and Mn⁴⁺ ions, while the latter acts as the diffusion barrier to inhibit grain growth and produce advantageous reactive electronic structures around the interface. The La-modified Mn₂O₃ oxide reached 90% conversion in toluene oxidation at 286 °C under the high WHSV of 240,000 mL g^–1 h^–1 and slightly increased to 327 °C after thermal aging at 800 °C. This work provides a versatile strategy for fabricating effective oxidation catalysts with high low-temperature activity and antisintering properties for industrial applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Trapping Properties of Iodine, Cesium, and Tellurium in Uranium Dioxide: A DFT+U Study","authors":"Mathieu Gascoin, Michel Freyss, Ibrahim Cheik Njifon","doi":"10.1021/acs.inorgchem.4c03096","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03096","url":null,"abstract":"We investigate the trapping properties of iodine, cesium, and tellurium in uranium dioxide, using the Hubbard-corrected density functional theory (DFT+<i>U</i>). In order to avoid the metastable states inherent to this method, we use the occupation matrix control (OMC) scheme, which also allows us to monitor the oxidation states of the different species. The most favorable trapping sites, oxidation states, and solubility of I, Cs, and Te are evaluated in stoichiometric UO₂. To that end, vacancy-like defects under various charge states, including uranium and oxygen vacancies, U–O divacancy and bound Schottky defects, as well as the interstitial position, are considered as potential trapping sites in UO₂. Te is found to exhibit a wide range of possible oxidation states, ranging from Te^– to Te⁴⁺, depending on the stable trapping site considered. For I and Cs, one predominant oxidation state for each fission product, namely, I^– and Cs⁺, is found. This behavior is mainly accommodated by the charge of the defects. By providing accurate trapping sites and oxidation states of volatile fission products in UO₂, this study is expected to contribute in the development of larger scale simulation methods, enabling a better prediction and mitigation of corrosion issues in nuclear fuel cladding.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"200 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Conformation and Bonding of Lanthanide(III) Trihalides LnX3 (Ln = La–Lu; X = F, Cl, Br): A Relativistic Local Vibrational Mode Study”","authors":"Barbara M. T. C. Peluzo, Renaldo T. Moura, Jr., Elfi Kraka","doi":"10.1021/acs.inorgchem.4c05069","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05069","url":null,"abstract":"The authors thank Robert Jordan for bringing to our attention that some columns in the original Tables 2 and 3 were switched. The correct Tables 2 and 3 on pages 22449 and 22450 are the following: Bond distance <i>r</i> is given in Å; <i>k</i>^<i>a</i>(<i>r</i>) is the local force constant associated with <i>r</i>, given in mdyn/Å; <i>H</i>(<b>r</b>_<i>b</i>) is the energy density, evaluated at each Ln–Cl bond critical point, given in Ha/ų; Δ⁽²⁾ is the 2^<i>nd</i> order stabilization energy accounting for charge transfers from fluorine lone pairs into the vacant lanthanide orbitals, given in kcal/mol; α is the α(Cl–Ln–Cl) angle, given in degrees; <i>k</i>^<i>a</i>(α) is the local force constant associated with α, given in mdyn/Å. β is the β(Cl–Ln–Cl–Cl) angle, given in degrees; <i>k</i>^<i>a</i>(β) is the local force constant associated with β, given in mdyn/Å LC: PBE0/MWB(46-60)(La–Lu)/def2-QZVPP(Cl). SC: PBE0/MWB28(La–Lu)/def2-QZVPP(Cl). NESC-2c: GPBE0/NESC/(23s16p12d6f)/[18s12p9d3f](La–Lu)/TZVPPall-2c(Cl). The following results obtained under SC formalism have been averaged: PrCl₃, NdCl₃, TbCl₃, and DyCl₃. Individual values are provided as Supporting Information. Bond distance <i>r</i> is given in Å; <i>k</i>^<i>a</i>(<i>r</i>) is the local force constant associated with <i>r</i>, given in mdyn/Å; <i>H</i>(<b>r</b>_<i>b</i>) is the energy density, evaluated at each Ln–Cl bond critical point, given in Ha/ų; Δ⁽²⁾ is the 2^<i>nd</i> order stabilization energy accounting for charge transfers from fluorine lone pairs into the vacant lanthanide orbitals, given in kcal/mol; α is the α(Br–Ln–Br) angle, given in degrees; <i>k</i>^<i>a</i>(α) is the local force constant associated with α, given in mdyn/Å. β is the β(Br–Ln–Br–Br) angle, given in degrees; <i>k</i>^<i>a</i>(β) is the local force constant associated with β, given in mdyn/Å LC: PBE0/MWB(46-60)(La–Lu)/def2-QZVPP(Br). SC: PBE0/MWB28(La–Lu)/def2-QZVPP(Br). NESC-2c: GPBE0/NESC/(23s16p12d6f)/[18s12p9d3f](La–Lu)/TZVPPall-2c(Br). The following results obtained under SC formalism have been averaged: PrBr₃, PmBr₃, and DyBr₃. Individual values are provided as Supporting Information. This article has not yet been cited by other publications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Uncoordinated Carboxyl Groups as Proton Sources in Polyoxometalate-Based Metal–Organic Frameworks Enhance Proton Conduction","authors":"Xin Zheng, Yu-Ming Cui, Ning-Hao Wang, Xue-Song Wu, Zhong-Min Su, Xing-Qi Han","doi":"10.1021/acs.inorgchem.4c04109","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04109","url":null,"abstract":"To select appropriate organic ligands is an effective strategy to enhance the proton conductivities of polyoxometalate-based metal–organic frameworks (POMOFs). Two new Dawson-type POMOFs, named CUST-961 and CUST-962, have been designed and synthesized via combining Htzbc selected by hard and soft acid and base theory and density functional theory calculation, transition metal ions, alkali metal ions (Na⁺ and K⁺), and Dawson-type polyoxometalates ([P₂W₁₈]^6–) under the hydrothermal method. Their stabilities under different temperatures and relative humidities (RHs) have been investigated through powder X-ray diffraction and thermogravimetric analysis. Both CUST-961 and CUST-962 exhibited excellent aqueous and thermal stabilities. The alternating current (AC) impedance spectrum tests revealed that the proton conductivity of CUST-961 could reach 1.4 × 10^–4 S cm^–1 at 95 °C and 98% RH, which is about 3 times that of CUST-962. The different proton conductivities between the two compounds are due to the fact that CUST-961 possesses more uncoordinated carboxylic acid groups, as confirmed by attenuated total reflection infrared spectroscopy and ¹H solid-state nuclear magnetic resonance spectroscopy, which can not only act as the proton source but also establish a richer hydrogen bonding network to enhance proton conduction. This work provides a new strategy and insight for the design and preparation of polyoxometalate-based proton conductive materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactivity Study of the Bis(phosphine)-Stabilized Antimony(I) Cation","authors":"Nilanjana Mukherjee, Vikas Kumar, Cem B. Yildiz, Moumita Majumdar","doi":"10.1021/acs.inorgchem.4c04257","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04257","url":null,"abstract":"The 5,6-Bis(diisopropylphosphino)acenaphthene <b>L</b>-stabilized Sb(I) cationic compound [LSb][OTf] (OTf = CF₃SO₃) <b>1</b> possessing two lone pairs of electrons on the Sb(I) center showed nucleophilic behavior toward methyl trifluoromethanesulfonate forming the oxidized product [LSbMe][OTf]₂ <b>2</b> (OTf = CF₃SO₃). Reaction of compound <b>1</b> with Lewis acids such as GaCl₃ and AlBr₃ led to changes in the counteranions only giving products [LSb][GaCl₄] <b>3</b> and [LSb][SbBr₄] <b>4</b>, respectively. A metathesis reaction was observed when compound <b>1</b> was reacted with PI₃. The Sb(I) cation in <b>1</b> underwent the metathesis reaction with the P(I) cation, forming the more stable product [LP][OTf] <b>5</b>. The Sb(I) center in <b>1</b> was completely oxidized to Sb(V) by reacting with two equivalents of <i>o</i>-chloranil to give the Bis(phosphine)-stabilized Bis(perchloro catecholato)stibonium cation [L(O₂C₆Cl₄)₂Sb][OTf] <b>6</b>. Both compounds <b>1</b> and <b>6</b> were employed as proof-of-concept Lewis acid catalysts for the hydrosilylation of <i>p</i>-methyl benzaldehyde. All the compounds were characterized using single-crystal X-ray diffraction analysis, multinuclear nuclear magnetic resonance spectroscopy, mass spectrometry, and absorbance spectroscopy. Density functional theory calculations were performed on the relevant compounds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"62 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Antithermal Quenching Behavior in 0D Inorganic Metal Halide Cs2InCl5(H2O) Mediated by Upconversion Emission","authors":"Maohao Yang, Wanyin Ge, Toshiharu Teranishi","doi":"10.1021/acs.inorgchem.4c04557","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04557","url":null,"abstract":"Inorganic metal halides (IMHs) often suffer from severe fluorescence thermal quenching, limiting their application at elevated temperatures. Therefore, the exploration of IMHs exhibiting antithermal quenching (ATQ) behavior is of great importance. In this study, we developed a green synthetic route using a solvent evaporation method to successfully synthesize the 0D IMHs Cs₂InCl₅(H₂O). By precise control over the doping ratios of Sb³⁺, Yb³⁺, and Er³⁺, unique dual-mode emission properties are obtained. As the temperature increases, the compound exhibited downconversion and upconversion luminescence, with relative sensitivity <i>S</i>_R-max values of 7.11% K^–1 and 1.21% K^–1, respectively. Particularly anomalous is the compound’s manifestation of an unconventional ATQ behavior during the upconversion process. <i>In situ</i> structural analysis confirmed that under high-temperature conditions, the 0D Cs₂InCl₅(H₂O) metal halide undergoes structural evolution, transitioning through a Cs₃In₂Cl₉ phase, which is responsible for the ATQ. This study provides experimental evidence for the abnormal ATQ of 0D metal halides, offering new inspiration for the multifunctionalization of 0D metal halides in high-temperature temperature sensing and dual-mode luminescence.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"239 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Experimental and Theoretical Investigations for Revealing the Influence of Cyclometalated Ligand Type on Protonolysis of Pt–Carbon Sites","authors":"Shabnam Borji, Mina Sadeghian, Mohsen Golbon Haghighi","doi":"10.1021/acs.inorgchem.4c04190","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04190","url":null,"abstract":"This study investigates possible pathways arising from the reaction of anionic K[Pt(C^N)(<i>p</i>-MeC₆H₄)(CN)] complexes, C^N = 2-phenylpyridinate (ppy) and 7,8-benzo[h]quinolate (bzq), with trifluoroacetic acid (TFA), which has been employed in both experimental and computational approaches. Experimental studies clarify that the products of the protonolysis reaction can vary in the K[Pt(C^N)(<i>p</i>-MeC₆H₄)(CN)] complex depending on the type of the cyclometalated ligand. In the cyclometalated complex with ppy, only one product was observed, resulting from the cleavage of the Pt–C_ppy bond of the cyclometalated ligand. Notably, when K[Pt(bzq)(<i>p</i>-MeC₆H₄)(CN)] reacts with trifluoroacetic acid, the protonolysis of both Pt–C_{<i>p</i>-tolyl} and Pt–C_bzq occurs in nearly equal proportions. The results indicate that the S_E2 mechanism plays a primary role in the emergence of the products. Additionally, the experimental measurements did not detect any evidence for HCN creation, which is rooted in the high energy barrier and complex mechanism of protonation of the Pt–C_sp(CN) in contrast to Pt–C_sp²(<i>p</i>-MeC₆H₄) and Pt–C_sp²(C^N) bonds. Comparison of the C–H bond protonolysis reaction on the C_sp, C_sp², and C_sp³ atoms in the investigated complexes has been carried out by substitution of the <i>p</i>-MeC₆H₄ ligand with a CH₃ ligand to form a [Pt(ppy)(CH₃)(CN)]⁻ complex. According to our density functional theory (DFT) calculations, this substitution leads to protonolysis of the Pt–C_C^N bond as the main product. The absence of the CH₄ product is due to the increase of the reaction barrier for the Pt–C_Me bond protonolysis and a decrease in steric hindrance by the presence of a CH₃ ligand.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}