Harbi Tomah AL-Masri, Suzan Mohammed Alrawashdeh, Akram Ali Almejled, Ziad moussa
The reaction of N‐(4‐methyl‐2‐pyridinyl)‐P,P‐diphenylphosphinous amide ligand 4‐Me‐C5H3N‐2‐NH(PPh2) (1) with M(CO)6 (M = Cr, Mo, W) in refluxing toluene afforded a mononuclear group 6B metal tetracarbonyls [M(CO)4{1‐κ2P,N}] (M = Cr(2), Mo(3), W(4) ). Complexes 2–4 were characterized by multinuclear NMR (1H, 13C and 31P NMR) and IR spectroscopy, and their structures were also determined by single crystal X‐ray diffraction. 2 and 4 represent the first examples of structurally characterized complexes of such ligands with group 6B metal carbonyls.
{"title":"Synthesis and crystal structures of novel group 6B metal carbonyl complexes with N‐(4‐methyl‐2‐ pyridinyl)‐P,P‐diphenylphosphinous amide ligand","authors":"Harbi Tomah AL-Masri, Suzan Mohammed Alrawashdeh, Akram Ali Almejled, Ziad moussa","doi":"10.1002/zaac.202400075","DOIUrl":"https://doi.org/10.1002/zaac.202400075","url":null,"abstract":"The reaction of N‐(4‐methyl‐2‐pyridinyl)‐P,P‐diphenylphosphinous amide ligand 4‐Me‐C5H3N‐2‐NH(PPh2) (1) with M(CO)6 (M = Cr, Mo, W) in refluxing toluene afforded a mononuclear group 6B metal tetracarbonyls [M(CO)4{1‐κ2P,N}] (M = Cr(2), Mo(3), W(4) ). Complexes 2–4 were characterized by multinuclear NMR (1H, 13C and 31P NMR) and IR spectroscopy, and their structures were also determined by single crystal X‐ray diffraction. 2 and 4 represent the first examples of structurally characterized complexes of such ligands with group 6B metal carbonyls.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506916","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}
K4[(IF5)6(HF2)4] was obtained from the reaction of K[HF2] with liquid IF5. The compound was analyzed by single crystal and powder X‐ray diffraction, Raman spectroscopy, and quantum‐chemical calculations. It contains the largest molecular IF5/HF2− complex anion known so far. Surprisingly, the crystal structure of the A4B compound can be related to the Hg4Pt structure type.
{"title":"The peculiar molecular [(IF5)6(HF2)4]4− anion of the compound K4[(IF5)6(HF2)4]","authors":"Björn Koch, Tim Florian Graubner, Florian Kraus","doi":"10.1002/zaac.202400085","DOIUrl":"https://doi.org/10.1002/zaac.202400085","url":null,"abstract":"K4[(IF5)6(HF2)4] was obtained from the reaction of K[HF2] with liquid IF5. The compound was analyzed by single crystal and powder X‐ray diffraction, Raman spectroscopy, and quantum‐chemical calculations. It contains the largest molecular IF5/HF2− complex anion known so far. Surprisingly, the crystal structure of the A4B compound can be related to the Hg4Pt structure type.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"180 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506918","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}
Jingyao Yang, Feiyu Lu, Wencui Li, Lu Zhang, Jingrui Yin, Mohd. Muddassir, Liming Fan
Based on the mixed ligands of 1,4‐bis(2,4,6‐tricarboxylpyrid‐5‐yl)benzene (H6BTPB) and 1,4‐bis(imidazol‐1‐yl)benzene (bib), a new cadmium(II) coordination polymer with the molecular formula of {[Cd(bib)(μ2‐H2O)(H2O)2](H4BTPB)0.5(bib)0.5}n (CdCP) was constructed under solvothermal condition, and displayed a 3D supramolecular structure expanded by the hydrogen bonds between the 1D [Cd(bib)(μ2‐H2O)(H2O)2]n ladder chain and the guests. Profiting from its superior stability and inherent luminescence, the prepared CdCP dispalyed great potential as a highly sensitive and selective luminescent sensor in trace detection of 3‐NT biomarker in both water and real bodily fluids through the luminescence quenching effects, with the Ksv and LODs being 2.408×105 M‐1 and 30.3 nM in water, 2.230×105 M‐1 and 44.7 nM in diluted urine, 2.249×105 M‐1 and 43.9 nM in diluted serum, respectively. Subsequent mechanism studies indicated the synergistic effect of internal filtering effect, photo‐induced electron transfer, and fluorescence resonance energy transfer determining the luminescence quenching response of CdCP towards 3‐NT biomarker.
{"title":"Practicality and Compatibility of Cd(II) Coordination Polymer as Luminescent Sensor in Selective and Sensitive Detection of 3‐Nitrotyrosine Biomarker","authors":"Jingyao Yang, Feiyu Lu, Wencui Li, Lu Zhang, Jingrui Yin, Mohd. Muddassir, Liming Fan","doi":"10.1002/zaac.202400065","DOIUrl":"https://doi.org/10.1002/zaac.202400065","url":null,"abstract":"Based on the mixed ligands of 1,4‐bis(2,4,6‐tricarboxylpyrid‐5‐yl)benzene (H6BTPB) and 1,4‐bis(imidazol‐1‐yl)benzene (bib), a new cadmium(II) coordination polymer with the molecular formula of {[Cd(bib)(μ2‐H2O)(H2O)2](H4BTPB)0.5(bib)0.5}n (CdCP) was constructed under solvothermal condition, and displayed a 3D supramolecular structure expanded by the hydrogen bonds between the 1D [Cd(bib)(μ2‐H2O)(H2O)2]n ladder chain and the guests. Profiting from its superior stability and inherent luminescence, the prepared CdCP dispalyed great potential as a highly sensitive and selective luminescent sensor in trace detection of 3‐NT biomarker in both water and real bodily fluids through the luminescence quenching effects, with the Ksv and LODs being 2.408×105 M‐1 and 30.3 nM in water, 2.230×105 M‐1 and 44.7 nM in diluted urine, 2.249×105 M‐1 and 43.9 nM in diluted serum, respectively. Subsequent mechanism studies indicated the synergistic effect of internal filtering effect, photo‐induced electron transfer, and fluorescence resonance energy transfer determining the luminescence quenching response of CdCP towards 3‐NT biomarker.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141516318","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}
{"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}
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