{"title":"In celebration of the 60th birthday of Rhett Kempe","authors":"Birgit Weber, Sven Rau","doi":"10.1002/zaac.202400124","DOIUrl":"https://doi.org/10.1002/zaac.202400124","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"193 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141516319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reaction of a sterically shielded Mg hydride complex, bearing a bulky β‐diketiminato (BDI) ligand, with CO2 leads to the formation of polynuclear complexes. CO2 not only inserts into the metal hydride bond yielding formate ions, but also adds onto the γ‐C of the BDI ligand. This reactivity gives rise to the formation of tri‐ and tetranuclear structures in THF, leading to a hexameric structure associated with a change in the coordination mode of the BDI ligand at 60 °C in THF within four days. The hexameric complex was isolated in high reproducible yield from the solution and characterized by X‐ray diffraction analysis. The reaction affording the hexameric complex was shown to be completed within 1 h at room temperature in toluene. Similar reactions of CO2 with a BDI calcium hydride complex proceeds less cleanly and a pure product could not be isolated.
带有笨重的 β-二乙酰亚氨基（BDI）配体的具有立体屏蔽作用的氢化镁络合物与二氧化碳反应，会形成多核络合物。二氧化碳不仅插入金属氢化物键产生甲酸根离子，还加入到 BDI 配体的 γ-C 上。这种反应性导致在四氢呋喃中形成三核和四核结构，并在四氢呋喃中 60 °C 的四天内形成与 BDI 配体配位模式变化相关的六聚体结构。从溶液中分离出的六聚体复合物具有很高的重复产率，并通过 X 射线衍射分析对其进行了表征。生成六聚体复合物的反应在室温甲苯中 1 小时内完成。二氧化碳与 BDI 氢化钙络合物的类似反应进行得不太顺利，无法分离出纯产物。
{"title":"Reaction of a Bulky β‐Diketiminato Magnesium Hydride with CO2 Yielding a Polynuclear Magnesium Cage Compound","authors":"Wimonsiri Huadsai, Laure Vendier, Matthias Westerhausen, Sébastien Bontemps","doi":"10.1002/zaac.202400070","DOIUrl":"https://doi.org/10.1002/zaac.202400070","url":null,"abstract":"The reaction of a sterically shielded Mg hydride complex, bearing a bulky β‐diketiminato (BDI) ligand, with CO2 leads to the formation of polynuclear complexes. CO2 not only inserts into the metal hydride bond yielding formate ions, but also adds onto the γ‐C of the BDI ligand. This reactivity gives rise to the formation of tri‐ and tetranuclear structures in THF, leading to a hexameric structure associated with a change in the coordination mode of the BDI ligand at 60 °C in THF within four days. The hexameric complex was isolated in high reproducible yield from the solution and characterized by X‐ray diffraction analysis. The reaction affording the hexameric complex was shown to be completed within 1 h at room temperature in toluene. Similar reactions of CO2 with a BDI calcium hydride complex proceeds less cleanly and a pure product could not be isolated.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"85 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single crystals of CaAl2Pt2, Ca2Al3Pt and Ca2AlPt2 were initially observed in an attempt to synthesize Ca3Al4Pt4. Their structures were determined using single‐crystal X‐ray diffraction experiments. While nominal CaAl2Pt2 (CaBe2Ge2 type, P4/nmm, a = 426.79(2), c = 988.79(6) pm, wR2 = 0.0679, 246 F2 values and 18 variables) and Ca2Al3Pt (Mg2Cu3Si type, P63/mmc, a = 561.46(5), c = 876.94(8) pm, wR2 = 0.0664, 214 F2 values and 13 variables) exhibit Al/Pt mixing, for Ca2AlPt2 (Ca2Ir2Si type, C2/c, a = 981.03(2) b = 573.74(1), c = 772.95(2) pm, β = 101.862(1)° wR2 = 0.0307, 2246 F2 values and 25 variables) no mixing was observed. Subsequently, the nominal compositions were targeted with synthetic attempts from the elements using arc‐melting and annealing techniques. For CaAl2Pt2 and Ca2Al3Pt always multi‐phase mixtures were observed while Ca2AlPt2 could be obtained as almost X‐ray pure material. Quantum‐chemical calculations were used to investigate the charge transfer in these compounds rendering them polar intermetallics with a designated [AlxPty]δ– polyanion and Caδ+ cations in the cavities of the polyanions.
{"title":"Nominal CaAl2Pt2 and Ca2Al3Pt – two new intermetallic compounds in the ternary system Ca–Al–Pt","authors":"Stefan Engel, Marcus Koch, Oliver Janka","doi":"10.1002/zaac.202400094","DOIUrl":"https://doi.org/10.1002/zaac.202400094","url":null,"abstract":"Single crystals of CaAl2Pt2, Ca2Al3Pt and Ca2AlPt2 were initially observed in an attempt to synthesize Ca3Al4Pt4. Their structures were determined using single‐crystal X‐ray diffraction experiments. While nominal CaAl2Pt2 (CaBe2Ge2 type, P4/nmm, a = 426.79(2), c = 988.79(6) pm, wR2 = 0.0679, 246 F2 values and 18 variables) and Ca2Al3Pt (Mg2Cu3Si type, P63/mmc, a = 561.46(5), c = 876.94(8) pm, wR2 = 0.0664, 214 F2 values and 13 variables) exhibit Al/Pt mixing, for Ca2AlPt2 (Ca2Ir2Si type, C2/c, a = 981.03(2) b = 573.74(1), c = 772.95(2) pm, β = 101.862(1)° wR2 = 0.0307, 2246 F2 values and 25 variables) no mixing was observed. Subsequently, the nominal compositions were targeted with synthetic attempts from the elements using arc‐melting and annealing techniques. For CaAl2Pt2 and Ca2Al3Pt always multi‐phase mixtures were observed while Ca2AlPt2 could be obtained as almost X‐ray pure material. Quantum‐chemical calculations were used to investigate the charge transfer in these compounds rendering them polar intermetallics with a designated [AlxPty]δ– polyanion and Caδ+ cations in the cavities of the polyanions.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"226 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141516320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Varre S. V. S. N. Swamy, Manoj Kumar, Felix Krischer, Kai-Stephan Feichtner, Bert Mallick, Viktoria H. Gessner
The synthesis of two stable monoylide‐substituted stannylenes of type YCNSnR [R = Cl (1) or N(SiMe3)2 (2), and YCN = Ph3P(CN)C] starting from the cyanido‐substituted α‐metallated ylide YCN‐K and SnCl2 or (SiMe3)2NSnCl is reported. Coordination of the cyano group to the tin center results in the dimerization of both stannylenes 1 and 2 in the solid state as well as in solution, where syn‐ and anti‐isomers are present. X‐ray diffraction analyses in combination with DFT calculations revealed that the π‐electron density of the ylide ligand is predominantly shifted into the cyano moiety rather than towards the tin center. This results in a strong preference of the dimers over the monomers, which is further emphasized by the reaction with 2,5‐di‐tert‐butylhydroquinone, which undergoes a [1+4] addition to the tin center to yield a spiro compound while preserving the cyclic core of the dimer. In contrast, phenyl isocyanate and dicyclohexylcarbodiimide insert into the Sn‐Cylide bond, ultimately leading to the cleavage of the dimer and the formation of monomeric stannylenes with an ylide‐substituted thioamidato and amidinato ligand, respectively.
{"title":"Synthesis and Reactivity of Amino(ylide)stannylenes","authors":"Varre S. V. S. N. Swamy, Manoj Kumar, Felix Krischer, Kai-Stephan Feichtner, Bert Mallick, Viktoria H. Gessner","doi":"10.1002/zaac.202400079","DOIUrl":"https://doi.org/10.1002/zaac.202400079","url":null,"abstract":"The synthesis of two stable monoylide‐substituted stannylenes of type YCNSnR [R = Cl (1) or N(SiMe3)2 (2), and YCN = Ph3P(CN)C] starting from the cyanido‐substituted α‐metallated ylide YCN‐K and SnCl2 or (SiMe3)2NSnCl is reported. Coordination of the cyano group to the tin center results in the dimerization of both stannylenes 1 and 2 in the solid state as well as in solution, where syn‐ and anti‐isomers are present. X‐ray diffraction analyses in combination with DFT calculations revealed that the π‐electron density of the ylide ligand is predominantly shifted into the cyano moiety rather than towards the tin center. This results in a strong preference of the dimers over the monomers, which is further emphasized by the reaction with 2,5‐di‐tert‐butylhydroquinone, which undergoes a [1+4] addition to the tin center to yield a spiro compound while preserving the cyclic core of the dimer. In contrast, phenyl isocyanate and dicyclohexylcarbodiimide insert into the Sn‐Cylide bond, ultimately leading to the cleavage of the dimer and the formation of monomeric stannylenes with an ylide‐substituted thioamidato and amidinato ligand, respectively.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"361 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Claus Feldmann, Maxime A. Bonnin, Michael D. Suedes
[Se3Cl3]2[SnCl6] (1) and [BMIm]2[Ga8As6Cl16O14] (2) are prepared by Lewis‐acid‐base reaction of SnCl2 with SeCl4 and As2O3 with GaCl3/[BMIm]Cl at room temperature and at 60 °C. 1 contains [ClSe–Se–SeCl2]+ cations with an Se3 unit and isolated octahedral [SnCl6]2– anions. The cation was yet only obtainable via Se0/Se4+ synproportionation in liquid SO2 with AsF5. The [Ga8As6Cl16O14]2– anion in 2 consists of two central edge‐sharing GaO6 octahedra, surrounded by pseudo‐tetrahedral AsO3 units and tetrahedral GaCl3O and GaCl2O2 units. Moreover, an almost planar central Ga4O4 ring surrounded by six GaAs2O3 rings is characteristic, which was not described before. The title compounds are characterized by X‐ray diffraction based on single crystals and powders, infrared spectroscopy, thermogravimetry, and optical spectroscopy.
{"title":"Lewis‐Acid‐Base Synthesis of [Se3Cl3]2[SnCl6] and [BMIm]2[Ga8As6Cl16O14]","authors":"Claus Feldmann, Maxime A. Bonnin, Michael D. Suedes","doi":"10.1002/zaac.202400092","DOIUrl":"https://doi.org/10.1002/zaac.202400092","url":null,"abstract":"[Se3Cl3]2[SnCl6] (1) and [BMIm]2[Ga8As6Cl16O14] (2) are prepared by Lewis‐acid‐base reaction of SnCl2 with SeCl4 and As2O3 with GaCl3/[BMIm]Cl at room temperature and at 60 °C. 1 contains [ClSe–Se–SeCl2]+ cations with an Se3 unit and isolated octahedral [SnCl6]2– anions. The cation was yet only obtainable via Se0/Se4+ synproportionation in liquid SO2 with AsF5. The [Ga8As6Cl16O14]2– anion in 2 consists of two central edge‐sharing GaO6 octahedra, surrounded by pseudo‐tetrahedral AsO3 units and tetrahedral GaCl3O and GaCl2O2 units. Moreover, an almost planar central Ga4O4 ring surrounded by six GaAs2O3 rings is characteristic, which was not described before. The title compounds are characterized by X‐ray diffraction based on single crystals and powders, infrared spectroscopy, thermogravimetry, and optical spectroscopy.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141516321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexander Missyul, Martin Kreuzer, Oleg Usoltsev, Maxim Arsentev, Mikhail Chislov
The double oxalates MI3[MIII(C2O4)3] possess rich crystallochemistry and can be used as precursors for various ceramic materials. The article discusses a case of Li3[Al(C2O4)3]. A series of previously unknown hydrates (Li3[Al(C2O4)3]·5.5H2O, Li3[Al(C2O4)3]·4H2O, Li3[Al(C2O4)3]·H2O) was found for this composition, their crystal structure and temperatures of mutual transformations determined. Transformation from Li3[Al(C2O4)3]·4H2O to Li3[Al(C2O4)3]·H2O was found to be accompanied by a change in the topology of the bonding network. Uniaxial negative thermal expansion was found for anhydrous Li3[Al(C2O4)3]. Thermal decomposition of Li3[Al(C2O4)3] was demonstrated to be a promising way to obtain precursors for aluminate ceramics.
{"title":"Lithium tris(oxalato)aluminate and its hydrates: structure, mutual transformations and thermal decomposition","authors":"Alexander Missyul, Martin Kreuzer, Oleg Usoltsev, Maxim Arsentev, Mikhail Chislov","doi":"10.1002/zaac.202400032","DOIUrl":"https://doi.org/10.1002/zaac.202400032","url":null,"abstract":"The double oxalates MI3[MIII(C2O4)3] possess rich crystallochemistry and can be used as precursors for various ceramic materials. The article discusses a case of Li3[Al(C2O4)3]. A series of previously unknown hydrates (Li3[Al(C2O4)3]·5.5H2O, Li3[Al(C2O4)3]·4H2O, Li3[Al(C2O4)3]·H2O) was found for this composition, their crystal structure and temperatures of mutual transformations determined. Transformation from Li3[Al(C2O4)3]·4H2O to Li3[Al(C2O4)3]·H2O was found to be accompanied by a change in the topology of the bonding network. Uniaxial negative thermal expansion was found for anhydrous Li3[Al(C2O4)3]. Thermal decomposition of Li3[Al(C2O4)3] was demonstrated to be a promising way to obtain precursors for aluminate ceramics.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"90 14","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heiko Ruppert, Till Schreyer, M. C. Dietl, Matthias Rudolph, Stephen K. Hashmi, L. Greb
Tetradentate meso‐octaalkylcalix[4]pyrroles are well‐established ligands in d‐ and f‐block chemistry. In contrast to the related porphyrins, the sp3‐hybridized meso‐carbon atoms linking the four pyrrole units result in highly divers coordination modes. We previously reported on the combination of this ligand system with Sn(II) centers yielding tetracoordinated stannate(II) anions which could be employed as electron‐rich, strong σ‐donor ligands in transition metal chemistry. With this work we are extending the coordination chemistry of meso‐octaethylcalix[4]pyrrolato stannate(II) [1]2− onto gold(I). Synthesis of mono‐ and dinuclear gold complexes reveal a new dynamic binding mode involving μ2‐bridging coordination of a pyrrole nitrogen atom to both Sn and Au. Single‐crystal X‐ray diffraction and variable temperature NMR spectroscopy combined with quantum mechanical computations and bond analysis tools shed light on the involved intermediates.
四价中-八烷基钙[4]吡咯是 d-和 f-嵌段化学中成熟的配体。与相关的卟啉不同，连接四个吡咯单元的 sp3 杂化中碳原子产生了高度多样化的配位模式。我们以前曾报道过将这种配体体系与锡（II）中心结合产生四配位锡酸（II）阴离子的情况，这种阴离子可在过渡金属化学中用作电子丰富的强σ供体配体。通过这项工作，我们扩展了中辛基钙[4]吡咯烷锡酸（II）[1]2- 与金（I）的配位化学。单核和双核金配合物的合成揭示了一种新的动态结合模式，涉及吡咯氮原子与锡和金的μ2桥式配位。单晶 X 射线衍射和变温核磁共振光谱与量子力学计算和键合分析工具相结合，揭示了所涉及的中间体。
{"title":"Dynamic Coordination Behavior of a Structurally Constrained, Nucleophilic Sn(II) Towards Gold(I)","authors":"Heiko Ruppert, Till Schreyer, M. C. Dietl, Matthias Rudolph, Stephen K. Hashmi, L. Greb","doi":"10.1002/zaac.202400081","DOIUrl":"https://doi.org/10.1002/zaac.202400081","url":null,"abstract":"Tetradentate meso‐octaalkylcalix[4]pyrroles are well‐established ligands in d‐ and f‐block chemistry. In contrast to the related porphyrins, the sp3‐hybridized meso‐carbon atoms linking the four pyrrole units result in highly divers coordination modes. We previously reported on the combination of this ligand system with Sn(II) centers yielding tetracoordinated stannate(II) anions which could be employed as electron‐rich, strong σ‐donor ligands in transition metal chemistry. With this work we are extending the coordination chemistry of meso‐octaethylcalix[4]pyrrolato stannate(II) [1]2− onto gold(I). Synthesis of mono‐ and dinuclear gold complexes reveal a new dynamic binding mode involving μ2‐bridging coordination of a pyrrole nitrogen atom to both Sn and Au. Single‐crystal X‐ray diffraction and variable temperature NMR spectroscopy combined with quantum mechanical computations and bond analysis tools shed light on the involved intermediates.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"92 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352595","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tsuyoshi Kato, Shintaro Takahashi, A. Baceiredo, N. Saffon‐Merceron
The hydrosilylation reactions of dihydrosilylium ion, stabilized by coordination of a σ‐donating Ni(0) fragment, has been investigated. This complex with two reactive sites, dihydrosilylium and Ni(0) centers, readily reacts with diphenylacetylene via a selective mono‐hydrosilylation reaction to afford the corresponding Ni(0)‐stabilized (hydro)(vinyl)silylium ion. In the case of ethylene, three equivalents of olefin are consumed to give a cationic Ni(II)‐complex featuring a Bu‐Si+‐NiII‐Et moiety with a NHC‐supported Si atom. DFT calculations indicate that the hydrosilylation proceeds by a classical (Chalk‐Harrod type) mechanism with the assistance of NHC ligand moving between Si and Ni centers according to their stabilization requirements.
研究人员对通过配位σ-供体镍（0）片段而稳定的二氢硅烷基离子的氢化反应进行了研究。这种具有两个反应位点（二氢硅烷基和 Ni(0) 中心）的配合物很容易通过选择性单氢硅烷化反应与二苯基乙炔发生反应，生成相应的 Ni(0) 稳定化（氢）（乙烯基）硅烷基离子。在乙烯的情况下，消耗三当量的烯烃，得到阳离子 Ni(II)- 复合物，该复合物具有一个 Bu-Si+-NiII-Et 分子和一个 NHC 支持的硅原子。DFT 计算表明，在 NHC 配体的帮助下，氢硅烷化反应是通过经典（Chalk-Harrod 型）机理进行的，NHC 配体根据稳定要求在 Si 和 Ni 中心之间移动。
{"title":"Hydrosilylation Reactions with a Dihydrosilylium Ion Stabilized by Coordination of a σ‐Donating Ni(0) Ligand","authors":"Tsuyoshi Kato, Shintaro Takahashi, A. Baceiredo, N. Saffon‐Merceron","doi":"10.1002/zaac.202400062","DOIUrl":"https://doi.org/10.1002/zaac.202400062","url":null,"abstract":"The hydrosilylation reactions of dihydrosilylium ion, stabilized by coordination of a σ‐donating Ni(0) fragment, has been investigated. This complex with two reactive sites, dihydrosilylium and Ni(0) centers, readily reacts with diphenylacetylene via a selective mono‐hydrosilylation reaction to afford the corresponding Ni(0)‐stabilized (hydro)(vinyl)silylium ion. In the case of ethylene, three equivalents of olefin are consumed to give a cationic Ni(II)‐complex featuring a Bu‐Si+‐NiII‐Et moiety with a NHC‐supported Si atom. DFT calculations indicate that the hydrosilylation proceeds by a classical (Chalk‐Harrod type) mechanism with the assistance of NHC ligand moving between Si and Ni centers according to their stabilization requirements.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"72 18","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141357917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marc Hunsicker, Johannes Krebs, Michael Zimmer, Bernd Morgenstern, Volker Huch, D. Scheschkewitz
The synthesis of the phosphorus‐capped heptaphenylsilsesquioxane T7Ph7P is reported. We show that, unlike previous examples, it readily forms Lewis acid‐base adducts with boranes of different steric demand and the FeCO4 fragment. All complexes were characterized by multinuclear NMR and IR spectroscopy in solution and the solid state. The molecular structures of the adducts with BPh3 and B(C6F5)3 were determined from XRD suitable single crystals. The relative conformation of the Ph and C6F5 rings in T7Ph7P‐B(C6F5)3 suggests favorable π‐interactions, stabilizing the adducts to such a degree that attempts to activate H2 or CO2 were unsuccessful.
{"title":"Synthesis and ligand properties of silsesquioxane‐caged phosphite T7Ph7P","authors":"Marc Hunsicker, Johannes Krebs, Michael Zimmer, Bernd Morgenstern, Volker Huch, D. Scheschkewitz","doi":"10.1002/zaac.202400068","DOIUrl":"https://doi.org/10.1002/zaac.202400068","url":null,"abstract":"The synthesis of the phosphorus‐capped heptaphenylsilsesquioxane T7Ph7P is reported. We show that, unlike previous examples, it readily forms Lewis acid‐base adducts with boranes of different steric demand and the FeCO4 fragment. All complexes were characterized by multinuclear NMR and IR spectroscopy in solution and the solid state. The molecular structures of the adducts with BPh3 and B(C6F5)3 were determined from XRD suitable single crystals. The relative conformation of the Ph and C6F5 rings in T7Ph7P‐B(C6F5)3 suggests favorable π‐interactions, stabilizing the adducts to such a degree that attempts to activate H2 or CO2 were unsuccessful.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"112 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141362365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hans Jürgen Meyer, Markus Stöbele, Albert T Schwarz
The new binary metal carbodiimide La2S2(CN2) was synthesized via solid‐state metathesis reaction. The crystal structure was solved and refined on basis of single‐crystal X‐ray diffraction data with space group C2/m. The structure is represented by a layered structure, based on alternating layers of lanthanum, sulfide, and carbodiimide units. A close resemblance of the structure with that of La2O2C2 is discussed, as well as the less‐common coordination number seven of the lanthanum atom.
通过固态偏合成反应合成了新型二元金属碳二亚胺 La2S2(CN2)。根据单晶 X 射线衍射数据解析并完善了晶体结构，其空间群为 C2/m。晶体结构表现为层状结构，由镧、硫化物和碳化二亚胺单元交替组成。本文讨论了该结构与 La2O2C2 结构的相似性，以及镧原子较少见的配位数 7。
{"title":"The Mixed‐Anion compound La2S2(CN2)","authors":"Hans Jürgen Meyer, Markus Stöbele, Albert T Schwarz","doi":"10.1002/zaac.202400038","DOIUrl":"https://doi.org/10.1002/zaac.202400038","url":null,"abstract":"The new binary metal carbodiimide La2S2(CN2) was synthesized via solid‐state metathesis reaction. The crystal structure was solved and refined on basis of single‐crystal X‐ray diffraction data with space group C2/m. The structure is represented by a layered structure, based on alternating layers of lanthanum, sulfide, and carbodiimide units. A close resemblance of the structure with that of La2O2C2 is discussed, as well as the less‐common coordination number seven of the lanthanum atom.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"121 20","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141360528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：