European Journal of Inorganic Chemistry最新文献

{"title":"Prolinol-Derived Phenoxy-Amidine Titanium Complexes in Asymmetric Silylcyanation of Aldehydes","authors":"Valentin Vaillant-Coindard,&nbsp;Jérôme Bayardon,&nbsp;Yoann Rousselin,&nbsp;Raluca Malacea-Kabbara,&nbsp;Jean-Thomas Pouzens,&nbsp;Paul Fleurat-Lessard,&nbsp;Pierre Le Gendre","doi":"10.1002/ejic.202400405","DOIUrl":"10.1002/ejic.202400405","url":null,"abstract":"<p>Three new tridentate phenoxy-amidine ligands (FA) have been prepared <i>via</i> the ring-opening of benzoxazole by 2-(methylamino)ethanol, <i>L</i>-prolinol and <i>L</i>-diphenylprolinol. Coordination studies of these FA ligands with Ti have led to the synthesis of the complexes (L1–L3)Ti(O^<i>i</i>Pr)₂ (<b>1 a</b>–<b>3 a</b>) and (L1–L3)TiCl₂(thf) (<b>1 b</b>–<b>3 b</b>). The solid state structures of the dichlorido FA−Ti complexes revealed a distorted octahedral geometry around the metallic centre provided by the FA ligand in <i>mer</i>-fashion, the two residual chloro ligands in <i>cis</i> arrangement and a THF molecule. The chiral Ti-FA complexes were shown to promote the asymmetric silylcyanation reaction. With benzaldehyde as substrate, the best catalyst was the dichlorido Ti complex <b>3 b</b> with a diphenylprolinol in the ligand backbone. It afforded the cyanhydrine with 68 % conversion and 74 % ee after 24 h in DCM at –20 °C. The diisopropoxy Ti complex <b>3 a</b> was remarkably active with pivalaldehyde as substrate, yielding the cyanosilylated product with 99 % conversion and 61 % ee after only 30 min at −60 °C.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 30","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400405","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Structure, and Reactivity of Ruthenium-Indane Complexes with Diphosphine Ligand","authors":"Masumi Itazaki,&nbsp;Natsumi Kitani,&nbsp;Yukako Dobashi,&nbsp;Kento Okabayashi,&nbsp;Hiroshi Nakazawa,&nbsp;Toshiyuki Moriuchi","doi":"10.1002/ejic.202400415","DOIUrl":"10.1002/ejic.202400415","url":null,"abstract":"<p>Ruthenium-indane complex, <i>fac-</i>[Ru(NCMe)₃(CO)₂(InCl₃)] <b>1Cl</b> reacted with 0.5 equiv. of dppe/dppp to afford dinuclear ruthenium-indane complexes linked by diphosphine ligand, [{Ru(NCMe)₂(CO)₂(InCl₃)}₂{μ₂-Ph₂P(CH₂)_nPPh₂}] (n=2: <b>3</b>, 3: <b>4</b>). On the other hand, the reaction of <i>fac-</i>[Ru(NCMe)₃(CO)₂(InCl₃)] <b>1Cl</b> with 1 equiv. of dppp afforded the corresponding chelate ruthenium(0) indane complex, [Ru(NCMe)(CO)₂(InCl₃)(dppp)] <b>5</b>. In the case of dppm, a chelate complex [Ru(NCMe)(CO)₂(InCl₃)(dppm)] <b>6</b> was formed <i>via</i> the dinuclear Ru complex [{Ru(NCMe)₂(CO)₂(InCl₃)}₂(μ₂-dppm)]. Complexes <b>1Cl</b>, <b>5</b>, and <b>6</b> showed a catalytic activity for double-hydrosilylation of MeCN. Complexes <b>3</b>–<b>6</b> were fully characterized using NMR measurements, elemental analyses, and the structures of <b>1Cl</b>, <b>3</b>, <b>5</b>, and <b>6</b> were determined by X-ray crystallography.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 29","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Characterization of (OC-6-33)-Dichloridobis((4-(13C2)ethoxy)-4-(13C4)oxobutanoato)bis((15N)ethylamine)platinum(IV). Time-Dependent NMR Spectroscopy and HPLC-MS Investigations on its Stability in Cell Culture Medium","authors":"Thomas Maier,&nbsp;Bernhard K. Keppler,&nbsp;Mathea S. Galanski,&nbsp;Hristo P. Varbanov","doi":"10.1002/ejic.202400348","DOIUrl":"10.1002/ejic.202400348","url":null,"abstract":"<p>In order to investigate the stability of an experimental anticancer platinum(IV) prodrug in cell culture media, (OC-6-33)-dichloridobis((4-ethoxy)-4-oxobutanoato)bis(ethylamine)-platinum(IV) was synthesized with ¹⁵N labeled equatorial and fully ¹³C labeled axial ligands. The title compound as well as its stability in cell culture media was investigated in depth by ¹H, ¹³C, ¹⁵N, and ¹⁹⁵Pt one- and two-dimensional NMR spectroscopy as well as HPLC-MS. Different platinum(IV) compounds as a result of hydrolysis were detected in cell culture media as main species. Besides hydrolysis of one or both equatorial chlorido ligands, also hydrolysis of the ester moiety in the axial ligands and release of ethanol could be observed. The different mono and dihydroxidoplatinum(IV) species were proven by ¹⁹⁵Pt and ¹³C NMR spectroscopy as well as HPLC coupled to MS and HRMS. Reduction of the title compound to the corresponding platinum(II) analog or reaction of the complex with ingredients of the cell culture media were not observed. In cell culture medium supplemented with fetal calf serum (FCS), the formation of hydrolysis species was slowed down by a factor of two.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 30","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400348","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structures and NMR Solution Dynamics of Diorganotin Complexes with Bulky Quadridentate Salen- and Salphen-Type Schiff Bases (N2O2) Incorporating Diazenylpyridyl Side Arms","authors":"Prof. Dr. Tushar S. Basu Baul,&nbsp;Swmkwr Brahma,&nbsp;Dr. Maheswara Rao Addepalli,&nbsp;Dr. Andrew Duthie,&nbsp;Abdallah G. Mahmoud,&nbsp;Prof. Dr. M. Fátima C. Guedes da Silva,&nbsp;Prof. Dr. Sean Parkin","doi":"10.1002/ejic.202400377","DOIUrl":"10.1002/ejic.202400377","url":null,"abstract":"<p>A series of six complexes [<i>n</i>-Bu₂Sn(L¹)]⋅S (S=Benzene/toluene, mixed/partial) (<b>1</b>), [Ph₂Sn(L¹)]_n⋅S (S=Benzene) (<b>2</b>), [Bz₂Sn(L¹)] (<b>3</b>), [<i>n</i>-Bu₂Sn(L²)]_n (<b>4</b>), [Ph₂Sn(L²)] (<b>5</b>) and [Bz₂Sn(L²)] (<b>6</b>) were synthesized using diorganotin(IV) oxide precursors and two new bis-Schiff bases containing N₂O₂ donor atoms. The Schiff bases, H₂L¹ and H₂L², were prepared by reacting ethane-1,2-diamine or benzene-1,2-diamine with 2-hydroxy-5-(pyridin-3-yldiazenyl)benzaldehyde in absolute ethanol. Compounds <b>1–6</b> were characterized by IR and NMR spectroscopies, as well as by solid-state single-crystal X-ray diffraction (except for <b>3</b> and <b>6</b>). In all the complexes the bis-Schiff bases occupy the equatorial positions and the R groups are in axial sites. However, while <b>1</b> and <b>5</b> are discrete molecules where the tin atoms adopt distorted octahedral geometries, <b>2</b> and <b>4</b> are monoperiodic polymers with the metal cations in pentagonal bipyramidal environments. Although solid state crystallographic results revealed asymmetrical molecular configurations, solution NMR studies proved symmetric arrangements for all the compounds. Tin NMR spectroscopy confirmed that all complexes are six-coordinate in solution, despite variations in solid-state coordination. Further analysis using Hirshfeld surface and fingerprint plots provided insights into intermolecular interactions in compounds <b>1</b>, <b>2</b>, <b>4</b>, and <b>5</b>. This comprehensive study underscores the structural diversity and solution-state dynamics of organotin(IV) complexes synthesized using novel Schiff bases.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 33","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Regiospecific Conversion of Aliphatic Allenes to Dithioacetals via Palladium-Catalyzed Double Hydrothiolation","authors":"Rajendr S. Thakuri,&nbsp;Yesmin A. Rina,&nbsp;Joseph A. R. Schmidt","doi":"10.1002/ejic.202400339","DOIUrl":"10.1002/ejic.202400339","url":null,"abstract":"<p>Unlike aromatic allenes, the hydrothiolation of aliphatic allenes has proven challenging for previously developed catalysts. Herein, a 3-iminophosphine supported palladium catalyst is shown to be highly effective for the double hydrothiolation of aliphatic allenes, producing dithioacetals in a regioselective and atom-efficient manner. The utility of this methodology is demonstrated for twelve new dithioacetals formed from aliphatic allenes and aryl thiols and isolated in moderate to excellent yields in all cases.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 29","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202400339","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868283","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Macrocycle with a Pair of endo‐Isocyanides and its Affinity to Gold(I)","authors":"Charlotte Kress, Daniel Häussinger, Patrick Zwick, Alessandro Prescimone, Marcel Mayor","doi":"10.1002/ejic.202400408","DOIUrl":"https://doi.org/10.1002/ejic.202400408","url":null,"abstract":"A pair of isocyanides pointing towards each other are fixed in a macrocyclic scaffold. The arrangement not only increases their local concentration, it should also enable their linear arrangement in coordination compounds. The macrocyclic diisocyanide ligand 1 is synthesized and fully characterized. Its interaction with gold(I) ions is investigated. While IR‐ and 1H‐NMR‐based titration experiments unraveled a stoichiometry of 2 Au(I) ions per macrocycle 1, the corresponding association constants are studied by UV‐Vis titration experiments. However, the values are above the method’s detection limits and only a lower boundary of an over‐all association constant is determined to be 3.0 x107 m‐1. The kinetics of the complex formation is further analyzed by NMR titration experiments and in spite of a change in the solvent, association constants about one order of magnitude larger than the lower limit determined by the UV‐Vis experiments are obtained.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":2.524,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Adjustment of Electronic (OMe and NO2) and Steric (CHPh2) Effects in Bis(imino)pyridinyliron Precatalysts for Producing High Molecular Weight Linear PE","authors":"Ayesha Razzaq,&nbsp;Yanping Ma,&nbsp;Qaiser Mahmood,&nbsp;Zexu Hu,&nbsp;Yizhou Wang,&nbsp;Song Zou,&nbsp;Aibo Zhou,&nbsp;Tongling Liang,&nbsp;Shaoliang Kong,&nbsp;Wen-Hua Sun","doi":"10.1002/ejic.202400380","DOIUrl":"10.1002/ejic.202400380","url":null,"abstract":"<p>Based on variations in steric and electronic substituents in the N-aryl unit, a set of five 2-[1-(arylimino)ethyl]-6-[1-(2-benzhydryl-4-nitro-6-methoxyphenylimino)ethyl]pyridyliron dichloride complexes (where aryl=2,6-dimethylphenyl (<b>Fe-Me₂</b>), 2,6-diethylphenyl (<b>Fe-Et₂</b>), 2,6-diisopropyl (<b>Fe-iPr₂</b>), 2,4,6-trimethylphenyl (<b>Fe-Me₃</b>), 2,6-diethyl-4-methylphenyl (<b>Fe-Et₂Me</b>)) were synthesized and investigated for ethylene polymerization. Their structures and compositions were confirmed by FTIR, elemental analysis, and X-ray diffraction analysis (<b>Fe-Et₂</b> and <b>Fe-iPr₂</b>), revealing a distorted square pyramidal geometry around the iron center. When activated in situ with MAO or MMAO, these iron complexes acted as highly active precatalysts, achieving activity levels up to 29.0×10⁶ g_PE mol_Fe⁻¹ h⁻¹ for a 5-min reaction at 60 °C. A notable characteristic of these precatalysts is their high thermal stability, maintaining significant activity (2.0×10⁶ g_PE mol_Fe⁻¹ h⁻¹) at temperatures up to 100 °C. Importantly, the incorporation of strong electron-withdrawing groups in the ligand structure favored the production of polyethylene with high molecular weights (up to 407.5 kg mol⁻¹) across various reaction conditions, surpassing those of most previously reported iron complexes. Moreover, less hindered iron precatalysts showed higher activity compared to more hindered ones. However, the trend reversed when comparing the molecular weight of obtained polyethylene: more sterically hindered precatalysts yielded higher molecular weight polymers. The molecular weight distributions ranged from monomodal to bimodal with broad dispersity. DSC thermograms and ¹H/¹³C NMR spectra of the polyethylene confirmed its highly linear microstructure, evidenced by sharp endothermic peaks and pronounced singlets for the −(CH₂)_n− repeating units.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 33","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Potassium by Thallium Substitution: Symmetry Transformation Through Site Competition in Coordination Compounds","authors":"Feodor F. Chausov,&nbsp;Nikolay V. Somov,&nbsp;Irina S. Kazantseva,&nbsp;Dmitriy S. Rybin","doi":"10.1002/ejic.202400330","DOIUrl":"10.1002/ejic.202400330","url":null,"abstract":"<p>The study focused on the nitrilo-tris-(methylene phosphonate) [K₂ntpH₄]₂ and [(K_1−<i>y</i>Tl_<i>y</i>)₂ntpH₄]₂ complexes, which are a series of isovalent substitutions. The crystals of [K₂ntpH₄]₂ are monoclinic and belong to the space group of symmetry P2₁/c with Z=4. When thallium substitutes potassium, the molecular structure remains the same, but the symmetry of the crystal packing changes to a triclinic system, space group of symmetry P<span></span><math></math>\u0000, with Z=2. One coordination polyhedra maintains an isometric configuration, while the other undergoes significant distortions. Polarization-selective coordination is observed, where the thallium(I) ion, which is easily polarizable, populates the highly distorted polyhedron. The low polarizable potassium ion populates the weakly distorted one. The crystal is formed with an average thallium fraction higher than the initial aqueous solution. This suggests that replacing potassium ions in the complex with thallium ions is energetically favourable. It could explain why thallium is toxic to intracellular enzymes and carriers of genetic information. The isovalent substitution of potassium made it possible to observe the step-by-step formation of a super-strong hydrogen bond, a phenomenon that is rarely detected under normal conditions. The O…O interatomic distance in the hydrogen bond decreases gradually from 2.55 Å for [K₂ntpH₄]₂ to 2.474 Å for [Tl₂ntpH₄]₂.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 28","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase Transition of a Chiral Lead-Free Hybrid Antimony(III) Halide Crystal","authors":"Jun-Chao Qi,&nbsp;Zhang-Tian Xia,&nbsp;Xin Shen,&nbsp;Hang Peng,&nbsp;Hui-Ping Chen,&nbsp;Yong-Ju Bai,&nbsp;Wei-Qiang Liao","doi":"10.1002/ejic.202400388","DOIUrl":"10.1002/ejic.202400388","url":null,"abstract":"<p>Chiral organic–inorganic hybrid lead halides have recently attracted great attention due to their unique chirality and diverse functional properties. However, they suffer from highly toxic lead, while lead-free chiral hybrid metal halides especially those with phase transitions remain sparse. Here, we report a new lead-free chiral metal halide crystal [<i>R</i>-3-fluoropiperidinium]₂SbCl₅ ([<i>R</i>-3-FPP]₂SbCl₅), which crystalizes in chiral <i>P</i>2₁2₁2₁ space group at 293 K and consists of chiral [3-FPP]⁺ cations and one-dimensional [SbCl₅]_<i>n</i>²⁻ zigzag chains of corner-sharing SbCl₆ octahedrons. Notably, [<i>R</i>-3-FPP]₂SbCl₅ undergoes an above room temperature phase transition at 313 K, which can be attributed to the order-disorder transition of both the organic [<i>R</i>-3-FPP]⁺ cation and inorganic [SbCl₅]²⁻ anions. In addition, [<i>R</i>-3-FPP]₂SbCl₅ also shows a broad band gap of 3.21 eV. This work promotes the exploration of chiral lead-free hybrid lead halides with phase transitions.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 30","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nature of Metal–Metal Bond in Group-V Dinuclear Metallaborane Compounds: Open-Shell–Open-Shell Vs Closed-Shell–Closed-Shell Interaction","authors":"Harsha S. Karnamkkott,&nbsp;Kartik Chandra Mondal","doi":"10.1002/ejic.202400252","DOIUrl":"10.1002/ejic.202400252","url":null,"abstract":"<p>The investigation of metal–metal bonding is interesting due to the captivating structural features, unique chemical reactivity and physical properties of this class of complexes. The synthesis of the complexes having metal–metal bonds started to explor after the isolation of the dianionic Re₂Cl₈²⁻, possessing quadruple bonds between two Re atoms. After that, several complexes containing multiple metal-metal bonds were synthesized, isolated and characterised. The bonding situation in the metallaboranes [(Cp*)₂M₂(B₂H₆)₂] of group-V elements (M) in the +3 oxidation state [M = V (<b>1</b>), Ta (<b>2</b>)] was investigated by the DFT, NBO, QTAIM calculations and further with Energy Decomposition Analyses coupled with Natural Orbital for Chemical Valence (EDA–NOCV). Even though the metallaboranes are isostructural, the nature of metal–metal bonding interaction was found to be different, revealing the presence of open-shell–open-shell interaction in divanadium compound while its Ta-analogue possesses closed-shell–closed-shell interaction between two tantalum atoms. However, EDA–NOCV analyses suggest that Ta^III−Ta^III bonding interactions are stronger than those of the divanadaborane analogue, having an intrinsic interaction energy of −247.6 kcal/mol (<b>2</b>), and the interaction energy leading to the formation of a V−V bond between two molecular fragments, is −192.5 kcal/mol (<b>1</b>). The bonding analyses indicate that the strength of the metal–metal bond becomes stronger as the metal becomes heavier which is due to the higher contribution from electrostatic stabilization energy. The pairwise orbital analysis of the metal–metal bond denotes significant dative interaction between two tantalum centres, contributing 52.6 % (<b>2</b>) to the total orbital interaction energy. The electron-sharing interaction energy has been computed to be 44.3 % for the divanadaborane analogue (<b>1</b>). Two Cp*⁻ ligands do not play significant role in the stabilization/destabilization of the V−V bond while the Ta−Ta bond is slightly destabilized by Cp*⁻ ligands. The electronic π-clound mostly fills empty orbitals on the metals, M = V and Ta. Further analyses show that the B₂H₆²⁻ unit drags out some amount of electron densities from the central M−M bond of both complexes, which are visible in the deformation densities. The chemical bonding between two V^III ions of two triplet V-complexes (<b>3–4</b>) was also investigated via EDA-NOCV analysis. The analysis concluded the existance an one electron bond between two vanadium centres (V^III−V^III). Also, the other unpaired electron of triplet fragments in <b>3/4</b> prefers to reside on the non-bonding orbital on one of the V-containing molecular fragments.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"27 33","pages":""},"PeriodicalIF":2.2,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}