Dithiocarbamates are monoanionic chelating ligands, easily prepared from CS2 and secondary or primary amines, that find widespread use in agriculture, medicine, materials science and coordination chemistry. This is (in part) due to their ability to stabilise metals in a wide range of oxidation states, a result of soft (dithiocarbamate) and hard (thioureide) resonance forms. However, in the many thousands of publications on dithiocarbamate chemistry, some common misconceptions have arisen, often being accepted as truth. In this perspective we address some of these in the hope that, moving forward, the wider community will better grasp the nuances of the chemistry of this important ligand type.
{"title":"Addressing misconceptions in dithiocarbamate chemistry","authors":"David Pugh, Graeme Hogarth","doi":"10.1039/d5dt01085c","DOIUrl":"https://doi.org/10.1039/d5dt01085c","url":null,"abstract":"Dithiocarbamates are monoanionic chelating ligands, easily prepared from CS2 and secondary or primary amines, that find widespread use in agriculture, medicine, materials science and coordination chemistry. This is (in part) due to their ability to stabilise metals in a wide range of oxidation states, a result of soft (dithiocarbamate) and hard (thioureide) resonance forms. However, in the many thousands of publications on dithiocarbamate chemistry, some common misconceptions have arisen, often being accepted as truth. In this perspective we address some of these in the hope that, moving forward, the wider community will better grasp the nuances of the chemistry of this important ligand type.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"61 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329395","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}
Abraham Debretsion, Szilvia Bunda, Norbert Lihi, Zoltán Garda, Sabine Van Doorslaer, Emese Kun, Tibor Csupász, Gyula Tircsó, Eva J Toth, Ferenc Krisztián Kálmán
In this study, we report the thermodynamic, kinetic, relaxation and structural features of the Mn(II) complex formed with a newly synthetized O-pyclen ligand bearing a malonate pendant. The thermodynamic stability of [Mn(OPMMA)] is lower (pMn = 6.27) than that reported for the Mn(II) chelates of OPC2A (pMn = 8.69) and 3,9-PC2A ligands (pMn = 8.64), and it dissociates faster than those at physiological conditions (t1/2 = 2.1 min). This behavior can be related to the assymetric structure of the ligand and the presence of an unsubstituted N donor in the macrocycle. DFT calculations revealed a capped trigonal prismatic coordination geometry for [Mn(OPMMA)], involving the coordination of the macrocyclic donor atomes, the two carboxylates of the malonate pendant arm as well as an inner spehere water molecule to Mn(II). The relaxivity values of [Mn(OPMMA)] (r1p = 3.48 and r2p = 5.85 mM–1s–1 at 20 MHz and 298K, respectively) are slightly higher than those found for [Mn(OPC2A)] and [Mn(3,9-PC2A)]. The water exchange rate (kex298 = (22.1±0.1)107 s–1) is 2-4-times higher than that of the [Mn(OPC2A)] and [Mn(3,9-PC2A)] complexes. The slightly higher rotational correlation time as compared to [Mn(OPC2A)] (τrH298 = 55±3 ps vs. 40 ps) can be related to the less compact structure of [Mn(OPMMA)].
{"title":"Stability and relaxometric characterization of a manganase(II) based macrocyclic complex containing malonate pendant","authors":"Abraham Debretsion, Szilvia Bunda, Norbert Lihi, Zoltán Garda, Sabine Van Doorslaer, Emese Kun, Tibor Csupász, Gyula Tircsó, Eva J Toth, Ferenc Krisztián Kálmán","doi":"10.1039/d5dt01056j","DOIUrl":"https://doi.org/10.1039/d5dt01056j","url":null,"abstract":"In this study, we report the thermodynamic, kinetic, relaxation and structural features of the Mn(II) complex formed with a newly synthetized O-pyclen ligand bearing a malonate pendant. The thermodynamic stability of [Mn(OPMMA)] is lower (pMn = 6.27) than that reported for the Mn(II) chelates of OPC2A (pMn = 8.69) and 3,9-PC2A ligands (pMn = 8.64), and it dissociates faster than those at physiological conditions (t1/2 = 2.1 min). This behavior can be related to the assymetric structure of the ligand and the presence of an unsubstituted N donor in the macrocycle. DFT calculations revealed a capped trigonal prismatic coordination geometry for [Mn(OPMMA)], involving the coordination of the macrocyclic donor atomes, the two carboxylates of the malonate pendant arm as well as an inner spehere water molecule to Mn(II). The relaxivity values of [Mn(OPMMA)] (r1p = 3.48 and r2p = 5.85 mM–1s–1 at 20 MHz and 298K, respectively) are slightly higher than those found for [Mn(OPC2A)] and [Mn(3,9-PC2A)]. The water exchange rate (kex298 = (22.1±0.1)107 s–1) is 2-4-times higher than that of the [Mn(OPC2A)] and [Mn(3,9-PC2A)] complexes. The slightly higher rotational correlation time as compared to [Mn(OPC2A)] (τrH298 = 55±3 ps vs. 40 ps) can be related to the less compact structure of [Mn(OPMMA)].","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329400","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}
Gopinath Sahoo, Sang Mun Jeong, Chandra Sekhar Rout
The progress of high-performance supercapacitor electrode based on emerging 2D materials have received tremendous attention due to their high power density (> 10 kW kg-1) and long charge-discharge cycle life (>105 cycles). Having discovered in 2015, 2D borophene has emerged as a unique material among Xenes due to its excellent electron mobility, metallic behaviour, thermal conductivity, Dirac nature, stronger and more flexible compared to graphene. Theoretical studies show that borophene possess high electron density near Fermi level which contribute to the enhanced charge storage capability and quantum capacitance. This review article aims to provide the recent development on supercapacitor applications of pristine 2D borophene and their hybrid nanostructures with other emerging suitable materials. Initially, the structural aspects of borophene is introduced and then the progress of borophene in supercapacitors is thoroughly discussed. In the end, current challenges associated with borophene synthesis and energy storage performance, device fabrications are highlighted. Furthermore, the possible solutions, and future perspectives are summarized.
{"title":"2D Borophene: An Emerging Material for Supercapacitor Applications","authors":"Gopinath Sahoo, Sang Mun Jeong, Chandra Sekhar Rout","doi":"10.1039/d5dt00950b","DOIUrl":"https://doi.org/10.1039/d5dt00950b","url":null,"abstract":"The progress of high-performance supercapacitor electrode based on emerging 2D materials have received tremendous attention due to their high power density (> 10 kW kg-1) and long charge-discharge cycle life (>105 cycles). Having discovered in 2015, 2D borophene has emerged as a unique material among Xenes due to its excellent electron mobility, metallic behaviour, thermal conductivity, Dirac nature, stronger and more flexible compared to graphene. Theoretical studies show that borophene possess high electron density near Fermi level which contribute to the enhanced charge storage capability and quantum capacitance. This review article aims to provide the recent development on supercapacitor applications of pristine 2D borophene and their hybrid nanostructures with other emerging suitable materials. Initially, the structural aspects of borophene is introduced and then the progress of borophene in supercapacitors is thoroughly discussed. In the end, current challenges associated with borophene synthesis and energy storage performance, device fabrications are highlighted. Furthermore, the possible solutions, and future perspectives are summarized.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"45 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329393","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}
Lucy Huffman, Anjana Seshadri, Christopher D. Hastings, William W. Brennessel, Ignacio Franco, Brandon R. Barnett
Chelating ligand platforms derived from tris(2-aminoethyl)amine (TREN) can facilitate low coordination numbers and provide opportunities to tune the steric and electronic profile of the secondary coordination sphere. Herein, we examine the ability of two related tris(amidate)amine ligands to stabilize low-coordinate complexes of trivalent iron, and further use molecular dynamics (MD) simulations to gain insight into the dynamics of both the primary and secondary coordination spheres. Our cavitand-inspired ligand allows for the isolation of four-coordinate FeLOCH2O via oxidation of the anionic and isostructural ferrous precursor, demonstrating how the secondary sphere macrocycle can promote the retention of an open coordination site. Through comparison with a non-macrocyclized tris(amidate)amine ligand, molecular dynamics (MD) simulations are used to garner insights into how this macrocycle alters coordination sphere dynamics. Additionally, both four-coordinate FeLOCH2O and five-coordinate Fe(DMF)LOMe are shown to be synthons for the trigonal bipyramidal ferric fluoride complexes [Fe(F)LOCH2O]– and [Fe(F)LOMe]–, respectively.
{"title":"Assessing structure and dynamics of iron complexes supported by tris(amidate)amine ligands","authors":"Lucy Huffman, Anjana Seshadri, Christopher D. Hastings, William W. Brennessel, Ignacio Franco, Brandon R. Barnett","doi":"10.1039/d5dt01284h","DOIUrl":"https://doi.org/10.1039/d5dt01284h","url":null,"abstract":"Chelating ligand platforms derived from tris(2-aminoethyl)amine (TREN) can facilitate low coordination numbers and provide opportunities to tune the steric and electronic profile of the secondary coordination sphere. Herein, we examine the ability of two related tris(amidate)amine ligands to stabilize low-coordinate complexes of trivalent iron, and further use molecular dynamics (MD) simulations to gain insight into the dynamics of both the primary and secondary coordination spheres. Our cavitand-inspired ligand allows for the isolation of four-coordinate FeL<small><sup>OCH2O</sup></small> via oxidation of the anionic and isostructural ferrous precursor, demonstrating how the secondary sphere macrocycle can promote the retention of an open coordination site. Through comparison with a non-macrocyclized tris(amidate)amine ligand, molecular dynamics (MD) simulations are used to garner insights into how this macrocycle alters coordination sphere dynamics. Additionally, both four-coordinate FeL<small><sup>OCH2O</sup></small> and five-coordinate Fe(DMF)L<small><sup>OMe</sup></small> are shown to be synthons for the trigonal bipyramidal ferric fluoride complexes [Fe(F)L<small><sup>OCH2O</sup></small>]<small><sup>–</sup></small> and [Fe(F)L<small><sup>OMe</sup></small>]<small><sup>–</sup></small>, respectively.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"45 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319704","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}
A series of ruthenium complexes bearing a CNC-type pincer ligand with different substituents (CF3, H, and OMe) were synthesized and characterized for visible-light-driven photocatalytic CO2 reduction. The photocatalytic reactions were conducted using [Ru(dmbpy)3]2+ as a photosensitizer and BI(OH)H as a sacrificial electron donor in a DMA-TEOA mixed solvent under LED light irradiation. The main product was formic acid, along with small amounts of CO and H2. Contrary to previous findings that Papish et al. reported, the catalyst with an electron-withdrawing CF3 substituent on the CNC ligand exhibited higher turnover number for formic acid production (TONHCOOH = 4742) compared to the electron-donating OMe substituent (TONHCOOH = 2152) after 24 hours of irradiation. Addition experiments revealed that the cessation of CO2 reduction was primarily due to the degradation of the photosensitizer rather than deactivation of the catalyst. ESI-MS analysis detected the formation of a carbonate complex prior to the photocatalytic reaction. This study provides insights into the effect of substituents on CNC pincer ligands in ruthenium complexes for photocatalytic CO2 reduction.
{"title":"Visible-light-driven photocatalytic CO2 reduction using ruthenium complexes having a CNC-type pincer ligand: comparison of substituent effect on a CNC ligand","authors":"Yasuhiro Arikawa, Momo Morinaga, Miyu Kubota, Kenichiro Omoto, Eri Sakuda, Keisuke Umakoshi","doi":"10.1039/d5dt00900f","DOIUrl":"https://doi.org/10.1039/d5dt00900f","url":null,"abstract":"A series of ruthenium complexes bearing a CNC-type pincer ligand with different substituents (CF<small><sub>3</sub></small>, H, and OMe) were synthesized and characterized for visible-light-driven photocatalytic CO<small><sub>2</sub></small> reduction. The photocatalytic reactions were conducted using [Ru(dmbpy)<small><sub>3</sub></small>]<small><sup>2+</sup></small> as a photosensitizer and BI(OH)H as a sacrificial electron donor in a DMA-TEOA mixed solvent under LED light irradiation. The main product was formic acid, along with small amounts of CO and H<small><sub>2</sub></small>. Contrary to previous findings that Papish et al. reported, the catalyst with an electron-withdrawing CF<small><sub>3</sub></small> substituent on the CNC ligand exhibited higher turnover number for formic acid production (TON<small><sub>HCOOH</sub></small> = 4742) compared to the electron-donating OMe substituent (TON<small><sub>HCOOH</sub></small> = 2152) after 24 hours of irradiation. Addition experiments revealed that the cessation of CO<small><sub>2</sub></small> reduction was primarily due to the degradation of the photosensitizer rather than deactivation of the catalyst. ESI-MS analysis detected the formation of a carbonate complex prior to the photocatalytic reaction. This study provides insights into the effect of substituents on CNC pincer ligands in ruthenium complexes for photocatalytic CO<small><sub>2</sub></small> reduction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"30 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312160","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}
In this study, we successfully synthesized an anhydrous crystalline material based on the lanthanide metal dysprosium coordinated with the sulfate ligand. This material exhibits a unique cumulative enhancement effect: during constant-temperature cycling tests, its conductivity increased significantly with repeated testing cycles. Under anhydrous conditions at 243°C during the 10th cycle, a conductivity of 1.2×10⁻³ S·cm⁻¹ was achieved, representing a three-order-of-magnitude improvement over the initial value of 5.7×10⁻⁶ S·cm⁻¹ observed in the first cycle at 100°C. We sincerely hope this work will provide actionable insights for the design of proton-conductive materials and stimulate further research enthusiasm toward novel proton-conductive systems.
{"title":"Cumulative Enhancement Effect of Proton Conductivity in the Possible Hydrogen Fuel Cell Material Dysprosium Sulfate","authors":"Jinxiang Yang, Jiasheng Wang, Bo Li, Yuqing Yan, Zhiwu Qiao, Haibo Liu, Yicong Zhu","doi":"10.1039/d5dt01177a","DOIUrl":"https://doi.org/10.1039/d5dt01177a","url":null,"abstract":"In this study, we successfully synthesized an anhydrous crystalline material based on the lanthanide metal dysprosium coordinated with the sulfate ligand. This material exhibits a unique cumulative enhancement effect: during constant-temperature cycling tests, its conductivity increased significantly with repeated testing cycles. Under anhydrous conditions at 243°C during the 10th cycle, a conductivity of 1.2×10⁻³ S·cm⁻¹ was achieved, representing a three-order-of-magnitude improvement over the initial value of 5.7×10⁻⁶ S·cm⁻¹ observed in the first cycle at 100°C. We sincerely hope this work will provide actionable insights for the design of proton-conductive materials and stimulate further research enthusiasm toward novel proton-conductive systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"24 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312165","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}
Deepika Verma, Kiran Gupta, Snober S. Mir, Om Prakash
Bismuth dithiocarbamate (Bi-DTC) complexes have emerged as promising candidates in the fight against cancer, attributed to their unique mechanisms of action and low toxicity compared to traditional metal-based therapies. With their sulfur-rich coordination sites, the dithiocarbamate (DTC) ligands facilitate versatile binding and structural diversity, enabling the formation of supramolecular assemblies with potent biological activity. While bismuth itself does not naturally exhibit biological functions, its dithiocarbamate derivatives have demonstrated notable efficacy as anticancer agents and antimicrobial and antiparasitic properties. In vitro and in vivo studies reveal that bismuth dithiocarbamates (Bi-DTC) can effectively induce apoptosis, suppress tumour growth, and overcome chemoresistance, positioning them as innovative therapeutic options. This review examines the synthesis strategies, biological mechanisms, and experimental evidence supporting the anticancer potential of these complexes. It also highlights their antimicrobial and antileishmanial activities, emphasising the role of antimicrobial properties in preventive and supportive therapies during cancer treatment. However, further investigations are essential to delineate their mechanisms of action and optimise their clinical applicability for cancer treatment.
{"title":"Bismuth dithiocarbamate complexes as anticancer agents and beyond: a comprehensive review","authors":"Deepika Verma, Kiran Gupta, Snober S. Mir, Om Prakash","doi":"10.1039/d5dt00656b","DOIUrl":"https://doi.org/10.1039/d5dt00656b","url":null,"abstract":"Bismuth dithiocarbamate (Bi-DTC) complexes have emerged as promising candidates in the fight against cancer, attributed to their unique mechanisms of action and low toxicity compared to traditional metal-based therapies. With their sulfur-rich coordination sites, the dithiocarbamate (DTC) ligands facilitate versatile binding and structural diversity, enabling the formation of supramolecular assemblies with potent biological activity. While bismuth itself does not naturally exhibit biological functions, its dithiocarbamate derivatives have demonstrated notable efficacy as anticancer agents and antimicrobial and antiparasitic properties. <em>In vitro</em> and <em>in vivo</em> studies reveal that bismuth dithiocarbamates (Bi-DTC) can effectively induce apoptosis, suppress tumour growth, and overcome chemoresistance, positioning them as innovative therapeutic options. This review examines the synthesis strategies, biological mechanisms, and experimental evidence supporting the anticancer potential of these complexes. It also highlights their antimicrobial and antileishmanial activities, emphasising the role of antimicrobial properties in preventive and supportive therapies during cancer treatment. However, further investigations are essential to delineate their mechanisms of action and optimise their clinical applicability for cancer treatment.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312162","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}
Roman V. Larkovich, Francis Bru, Maxime R. Vitale, Laurence Grimaud, Catherine S. J. Cazin
A novel electrochemical method for the preparation of Pd–NHC (N-heterocyclic carbene) catalysts has been developed. Unlike previously reported procedures, the present method does not employ soluble sacrificial anodes as a metal source but makes use of well-defined Pd-containing precursors instead. Importantly, oxygen was observed to play a key role acting as an electrogenerated base. A superoxide anion is formed via the reduction of oxygen at the cathode. The subsequent deprotonation of the imidazolium salts and reaction of NHCs with the Pd species occurs either in a sequential or in a concerted manner resulting in the formation of the final organopalladium product.
{"title":"Electrochemical synthesis of palladium N-heterocyclic carbene (NHC) complexes","authors":"Roman V. Larkovich, Francis Bru, Maxime R. Vitale, Laurence Grimaud, Catherine S. J. Cazin","doi":"10.1039/d5dt00575b","DOIUrl":"https://doi.org/10.1039/d5dt00575b","url":null,"abstract":"A novel electrochemical method for the preparation of Pd–NHC (N-heterocyclic carbene) catalysts has been developed. Unlike previously reported procedures, the present method does not employ soluble sacrificial anodes as a metal source but makes use of well-defined Pd-containing precursors instead. Importantly, oxygen was observed to play a key role acting as an electrogenerated base. A superoxide anion is formed <em>via</em> the reduction of oxygen at the cathode. The subsequent deprotonation of the imidazolium salts and reaction of NHCs with the Pd species occurs either in a sequential or in a concerted manner resulting in the formation of the final organopalladium product.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"36 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312156","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}
Carboranyl-diphosphenes {1-P-2-[C(tBu)=N(Ar)]-1,2-C2B10H10}2 [Ar = Dmp (6) or Ph (7); Dmp = 2,6-Me2C6H3, Ph = C6H5] are prepared in good yields by the reduction of iminocarboranyldichlorophosphines 1-PCl2-2-[C(tBu)=N(Ar)]-1,2-C2B10H10 [where Ar = Dmp (4) or Ph (5)] with potassium graphite (KC8) in THF. Compunds 6 and 7 have similar dimeric structures in solid-state as confirmed by single crystal X-ray analyses. Their solution structures are, however, different on the basis of 31P NMR studies, which could be ascribed to steric effects of Dmp over Ph. As a result, 6 and 7 exhibit different coordination chemistry toward W(CO)5(THF). On the other hand, they show similar properties with oxdizing agents, giving a variety of phosphorus(III) compounds. The results indicate that 6 dissociates into carboranyl phosphinidene in THF.
{"title":"Carboranyl Diphosphenes: Synthesis, Structure and Reactivity","authors":"Tek Long Chan, Jie Zhang, Zuowei Xie","doi":"10.1039/d5dt01239b","DOIUrl":"https://doi.org/10.1039/d5dt01239b","url":null,"abstract":"Carboranyl-diphosphenes {1-P-2-[C(tBu)=N(Ar)]-1,2-C2B10H10}2 [Ar = Dmp (6) or Ph (7); Dmp = 2,6-Me2C6H3, Ph = C6H5] are prepared in good yields by the reduction of iminocarboranyldichlorophosphines 1-PCl2-2-[C(tBu)=N(Ar)]-1,2-C2B10H10 [where Ar = Dmp (4) or Ph (5)] with potassium graphite (KC8) in THF. Compunds 6 and 7 have similar dimeric structures in solid-state as confirmed by single crystal X-ray analyses. Their solution structures are, however, different on the basis of 31P NMR studies, which could be ascribed to steric effects of Dmp over Ph. As a result, 6 and 7 exhibit different coordination chemistry toward W(CO)5(THF). On the other hand, they show similar properties with oxdizing agents, giving a variety of phosphorus(III) compounds. The results indicate that 6 dissociates into carboranyl phosphinidene in THF.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312157","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}
Nicole Willeit, Tim Kratky, Viktor Hlukhyy, Sebastian Guenther, Thomas F Fässler
Catalytic reactions with metalated Zintl cluster as catalysts are an increasing research field, whereby the concept of heterogeneous single site catalysis is transferred towards homogeneous reactions, leading to so called single site homogeneous catalysts (SSHoCs). A synthetic protocol for three cluster compounds [Hyp3Ge9Ir(CO)PR3] ((Hyp = Si{SiMe3}3; R = Ph, ptolyl, Me; 1 3) is presented, in which the iridium atom is embedded in the polyhedral cluster surface. The products are characterized by NMR, IR as well as LIFDI/MS, and also structurally characterized for R = Ph by single crystal X ray structure determination comprising a closo [Ge9Ir] cluster. The exchange of the phosphine ligand of 1 in solution, which is regarded as an important step to create the active site, is investigated for various phosphines. In subsequent reactions oxidative addition of Si H bonds of primary and secondary silanes SiHR2R´ (R/R´ = H/Ph, H/pMePh, H/p{OMe}Ph, H/p{NMe2}Ph, Ph/H) to the Ir atom is investigated. The addition reaction is directly monitored by NMR spectroscopy. Additionally, LIFDI/MS, IR spectroscopy, and single crystal structure determination of the addition products confirm the reaction. X-ray photoelectron spectroscopy XPS reveals that the transition metal atom and the Ge atoms of the supporting cluster have a low oxidation state.
{"title":"Oxidative addition of Si H bonds to metal-decorated Zintl clusters [Hyp3Ge9Ir(CO)PR3] (R = Ph, ptolyl, Me)","authors":"Nicole Willeit, Tim Kratky, Viktor Hlukhyy, Sebastian Guenther, Thomas F Fässler","doi":"10.1039/d5dt01147g","DOIUrl":"https://doi.org/10.1039/d5dt01147g","url":null,"abstract":"Catalytic reactions with metalated Zintl cluster as catalysts are an increasing research field, whereby the concept of heterogeneous single site catalysis is transferred towards homogeneous reactions, leading to so called single site homogeneous catalysts (SSHoCs). A synthetic protocol for three cluster compounds [Hyp3Ge9Ir(CO)PR3] ((Hyp = Si{SiMe3}3; R = Ph, ptolyl, Me; 1 3) is presented, in which the iridium atom is embedded in the polyhedral cluster surface. The products are characterized by NMR, IR as well as LIFDI/MS, and also structurally characterized for R = Ph by single crystal X ray structure determination comprising a closo [Ge9Ir] cluster. The exchange of the phosphine ligand of 1 in solution, which is regarded as an important step to create the active site, is investigated for various phosphines. In subsequent reactions oxidative addition of Si H bonds of primary and secondary silanes SiHR2R´ (R/R´ = H/Ph, H/pMePh, H/p{OMe}Ph, H/p{NMe2}Ph, Ph/H) to the Ir atom is investigated. The addition reaction is directly monitored by NMR spectroscopy. Additionally, LIFDI/MS, IR spectroscopy, and single crystal structure determination of the addition products confirm the reaction. X-ray photoelectron spectroscopy XPS reveals that the transition metal atom and the Ge atoms of the supporting cluster have a low oxidation state.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312161","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}
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