Hannes Lukas Jacob, Jan Cramer, Robin Guthardt, Clemens Bruhn, Ulrich Siemeling
The diaminoferrocene derivative fc[NH(BMes2)]2 (1H2; fc = 1,1’‐ferrocenylene, Mes = mesityl) was prepared from fc(NH2)2 and Mes2BCl and used for the preparation of the N‐heterocyclic tetrylenes fc{[N(BMes2)]2E} (1E, E = Ge, Sn) via the sodium amide fc[NNa(BMes2)]2 (1Na2), which was obtained from 1H2 and NaN(SiMe3)2. 1H2 is inert towards LiN(SiMe3)2 or nBuLi. Its reaction with nBuLi in the presence of TMEDA afforded the TMEDA‐coordinated lithium amide 1Li2(TMEDA)2. Crystallisation of 1Na2 from THF furnished the adduct 1Na2(THF)3. The reaction of 1Na2 with Me3SiCl afforded 1(SiMe3)2. Attempts to obtain the thiourea fc{[N(BMes2)]2C=S} (1C=S) from 1Na2 and Cl2C=S were not successful. 1C=S is accessible from fc(NH3)Cl2, which is transformed to fc[(NH)2C=S] (2) by reaction with Cl2C=S and NEt3 (4 equiv.), followed by conversion of 2 to fc{[N(SiMe3)]2C=S} (3) with Me3SiCl and NEt3 (2 equiv.) and subsequent reaction of 3 with Mes2BCl. All new compounds except 1Na2 and 2 were structurally characterised by single‐crystal X‐ray diffraction. The N‐boryl substituents of 1E compete efficiently with the EII atom for nitrogen π‐donation, causing comparatively long EII–N bonds and small EII bond angles. 1C=S contains a four‐membered BNCS ring due to intramolecular adduct formation involving the Lewis basic S atom and a Lewis acidic B atom.
{"title":"An N‐Heterocyclic Germylene and Stannylene with a 1,1’‐Ferrocenylene Backbone and Dimesitylboryl N‐Substituents","authors":"Hannes Lukas Jacob, Jan Cramer, Robin Guthardt, Clemens Bruhn, Ulrich Siemeling","doi":"10.1002/zaac.202400111","DOIUrl":"https://doi.org/10.1002/zaac.202400111","url":null,"abstract":"The diaminoferrocene derivative fc[NH(BMes2)]2 (1H2; fc = 1,1’‐ferrocenylene, Mes = mesityl) was prepared from fc(NH2)2 and Mes2BCl and used for the preparation of the N‐heterocyclic tetrylenes fc{[N(BMes2)]2E} (1E, E = Ge, Sn) via the sodium amide fc[NNa(BMes2)]2 (1Na2), which was obtained from 1H2 and NaN(SiMe3)2. 1H2 is inert towards LiN(SiMe3)2 or nBuLi. Its reaction with nBuLi in the presence of TMEDA afforded the TMEDA‐coordinated lithium amide 1Li2(TMEDA)2. Crystallisation of 1Na2 from THF furnished the adduct 1Na2(THF)3. The reaction of 1Na2 with Me3SiCl afforded 1(SiMe3)2. Attempts to obtain the thiourea fc{[N(BMes2)]2C=S} (1C=S) from 1Na2 and Cl2C=S were not successful. 1C=S is accessible from fc(NH3)Cl2, which is transformed to fc[(NH)2C=S] (2) by reaction with Cl2C=S and NEt3 (4 equiv.), followed by conversion of 2 to fc{[N(SiMe3)]2C=S} (3) with Me3SiCl and NEt3 (2 equiv.) and subsequent reaction of 3 with Mes2BCl. All new compounds except 1Na2 and 2 were structurally characterised by single‐crystal X‐ray diffraction. The N‐boryl substituents of 1E compete efficiently with the EII atom for nitrogen π‐donation, causing comparatively long EII–N bonds and small EII bond angles. 1C=S contains a four‐membered BNCS ring due to intramolecular adduct formation involving the Lewis basic S atom and a Lewis acidic B atom.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"38 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608628","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}
Aynura Mammadova, Clemens Bruhn, Rudolf Pietschnig
Reaction of two equivalents of ((CH3)3Si)2C(C6H5)SLi·3THF with SnCl2·IPr (IPr=:C[N(Diip)C(H)]2, Diip= 2,6 i‐(CH3)2CH(C6H5) led to fragmentation of the organolithium component and gave IPr·Sn(SPh)2, compound 3. The latter compound has been further prepared from Ph‐SSi(CH3)3 whereas disproportionation of the Sn(II) species was observed when starting from Ph‐SLi. Stannylene adduct 3 has been characterized spectroscopically and its structure was explored with single crystal X‐ray diffraction (SCXRD). The carbene donor in 3 can be displaced by chloride upon formal HCl addition giving rise to the ionic stannylene adduct 3a IPr+[SnCl(SPh)2]‐, the structure of which was investigated with SCXRD as well.
{"title":"Synthesis and characterization of NHC stabilized bis(phenylsulfanyl)stannylene","authors":"Aynura Mammadova, Clemens Bruhn, Rudolf Pietschnig","doi":"10.1002/zaac.202400119","DOIUrl":"https://doi.org/10.1002/zaac.202400119","url":null,"abstract":"Reaction of two equivalents of ((CH3)3Si)2C(C6H5)SLi·3THF with SnCl2·IPr (IPr=:C[N(Diip)C(H)]2, Diip= 2,6 i‐(CH3)2CH(C6H5) led to fragmentation of the organolithium component and gave IPr·Sn(SPh)2, compound 3. The latter compound has been further prepared from Ph‐SSi(CH3)3 whereas disproportionation of the Sn(II) species was observed when starting from Ph‐SLi. Stannylene adduct 3 has been characterized spectroscopically and its structure was explored with single crystal X‐ray diffraction (SCXRD). The carbene donor in 3 can be displaced by chloride upon formal HCl addition giving rise to the ionic stannylene adduct 3a IPr+[SnCl(SPh)2]‐, the structure of which was investigated with SCXRD as well.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"154 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608627","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}
Fu-Wei Zheng, Lin Hua, Zhi-Yong He, Feng Geng, Yan Li, Long Wang, Xiang-Jun Zhu, Guo-Fang Li, Xian-Ying Duan, Hui-Qing Zhang, Hai-Tao Chen
Two butterfly‐like binuclear Gadolinium(III) (Gd) complex [Gd2(L1)2(H2L3)2(NO3)2] (1) and [Gd2(L2)2(H2L3)2(NO3)2] (2) were obtained by using 2‐hydroxybenzaldehyde or 2‐hydroxy‐1‐naphthaldehyde, 2‐aminophenol, pyridin‐2‐ylmethanamine and Gd(NO3)3·6H2O in CH3CN (H2L1 = (E)‐2‐((2‐hydroxybenzylidene)amino)phenol, H2L2 = (E)‐1‐(((2‐hydroxyphenyl)imino)methyl)naphthalen‐2‐ol, H2L3 = pyridin‐2‐ylmethanamine). Structural analysis suggests that all the ligands as protective units protect the central Gd(III) ions at the periphery. Magnetization studies exhibited magnetocaloric effect of 14.45 J·kg−1·K−1 at 4 K under ΔH = 7 T for complex 1 and 12.69 J·kg−1·K−1 at 2 K under ΔH = 7 T for complex 2. In complexes 1 and 2, although the coordination configurations are the same, the significant difference in MCE may be due to the adjustments of the peripheral ligands leading to changes in the coordination field strength. The electron affinity of the ligands can impact the interaction between the ligands and Gd(III) ions.
{"title":"Binuclear Gadolinium Complex by One‐Pot Method: Structure and Magnetic Property","authors":"Fu-Wei Zheng, Lin Hua, Zhi-Yong He, Feng Geng, Yan Li, Long Wang, Xiang-Jun Zhu, Guo-Fang Li, Xian-Ying Duan, Hui-Qing Zhang, Hai-Tao Chen","doi":"10.1002/zaac.202300238","DOIUrl":"https://doi.org/10.1002/zaac.202300238","url":null,"abstract":"Two butterfly‐like binuclear Gadolinium(III) (Gd) complex [Gd2(L1)2(H2L3)2(NO3)2] (1) and [Gd2(L2)2(H2L3)2(NO3)2] (2) were obtained by using 2‐hydroxybenzaldehyde or 2‐hydroxy‐1‐naphthaldehyde, 2‐aminophenol, pyridin‐2‐ylmethanamine and Gd(NO3)3·6H2O in CH3CN (H2L1 = (E)‐2‐((2‐hydroxybenzylidene)amino)phenol, H2L2 = (E)‐1‐(((2‐hydroxyphenyl)imino)methyl)naphthalen‐2‐ol, H2L3 = pyridin‐2‐ylmethanamine). Structural analysis suggests that all the ligands as protective units protect the central Gd(III) ions at the periphery. Magnetization studies exhibited magnetocaloric effect of 14.45 J·kg−1·K−1 at 4 K under ΔH = 7 T for complex 1 and 12.69 J·kg−1·K−1 at 2 K under ΔH = 7 T for complex 2. In complexes 1 and 2, although the coordination configurations are the same, the significant difference in MCE may be due to the adjustments of the peripheral ligands leading to changes in the coordination field strength. The electron affinity of the ligands can impact the interaction between the ligands and Gd(III) ions.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"12 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608642","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}
Uli Kazmaier, Alexander Horn, Emanuel Papadopoulos, Thorsten Kinsinger, Jennifer Greve, Etienne Bickel, Stavroula Pachoula
Matteson homologation with sodium azide in DMF proved to be an excellent highly stereoselective tool for the synthesis of complex α‐azido and α‐amino acids. Both enantiomers are easily accessible via the choice of the chiral boronic ester auxiliary.
{"title":"Stereoselective Synthesis of α‐Azido Esters and α‐Amino Acid Derivatives via Matteson Homologation of Boronic Esters","authors":"Uli Kazmaier, Alexander Horn, Emanuel Papadopoulos, Thorsten Kinsinger, Jennifer Greve, Etienne Bickel, Stavroula Pachoula","doi":"10.1002/zaac.202400113","DOIUrl":"https://doi.org/10.1002/zaac.202400113","url":null,"abstract":"Matteson homologation with sodium azide in DMF proved to be an excellent highly stereoselective tool for the synthesis of complex α‐azido and α‐amino acids. Both enantiomers are easily accessible via the choice of the chiral boronic ester auxiliary.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608640","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}
Molecular cages that contain silicon are highly versatile and stable materials with great potential for various scientific and technological applications due to their ability to form stable three‐dimensional frameworks. The synthesis of 2,2,3,3,5,5,6,6,7,7,8,8‐dodecamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane has already been reported and its modifications at the CH moiety have been demonstrated to afford varied functionality. Here, we present the synthesis and characterization of 2,2,3,3‐tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane, which is a phenyl‐substituted analogue of such a silicon‐containing cage. The Ph‐substituted Si‐containing cage exhibits a low‐lying LUMO due to the hyper‐conjugation including Si–Si, Si–C σ*‐orbitals, and π(phenyl)‐orbitals, which results in a remarkable bathochromic shift in the UV‐vis absorption spectrum.
{"title":"Synthesis of 2,2,3,3‐Tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane – a Phenyl‐substituted Silicon‐containing Cage","authors":"Koichi Sato, Takahiro Sasamori","doi":"10.1002/zaac.202400115","DOIUrl":"https://doi.org/10.1002/zaac.202400115","url":null,"abstract":"Molecular cages that contain silicon are highly versatile and stable materials with great potential for various scientific and technological applications due to their ability to form stable three‐dimensional frameworks. The synthesis of 2,2,3,3,5,5,6,6,7,7,8,8‐dodecamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane has already been reported and its modifications at the CH moiety have been demonstrated to afford varied functionality. Here, we present the synthesis and characterization of 2,2,3,3‐tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane, which is a phenyl‐substituted analogue of such a silicon‐containing cage. The Ph‐substituted Si‐containing cage exhibits a low‐lying LUMO due to the hyper‐conjugation including Si–Si, Si–C σ*‐orbitals, and π(phenyl)‐orbitals, which results in a remarkable bathochromic shift in the UV‐vis absorption spectrum.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608641","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}
A new MOF, named UoC‐11 (UoC = University of Cologne, [Mg4(3F‐BTB)2(OAc)2(DMF)6] · DMF), based on a fluorinated BTB (4,4′,4″‐benzene‐1,3,5‐triyl‐tris‐(benzoate)) derivative and Mg cations was synthesized incorporating additional acetate anions. Its crystal structure was determined from single crystal X‐ray diffraction data (P21/c, Z = 4). It consists of one‐dimensional Mg‐SBUs (strands), interconnected perpendicularly by tritopic linkers forming a dense two‐fold interpenetrating 3D network. Thus, only very small voids are formed which are fully occupied by the solvent. After activation at 150 °C (24 hours), no meaningful N2 adsorption was observed. Compared to the Ca and Sr analogues UoC‐9, UoC‐11 does not exhibit a crystal sponge behaviour. Thermal analysis (TGA) shows a release of all solvent molecules up to ~280 °C and the decomposition of the framework starts above 300 °C.
以氟化 BTB（4,4′,4″-苯-1,3,5-三基-（苯甲酸酯））衍生物和镁阳离子为基础，结合额外的醋酸阴离子，合成了一种新的 MOF，命名为 UoC-11（UoC = 科隆大学，[Mg4(3F-BTB)2(OAc)2(DMF)6] - DMF）。根据单晶 X 射线衍射数据（P21/c，Z = 4）确定了其晶体结构。它由一维 Mg-SBU（链）组成，通过三位连接体垂直相互连接，形成一个致密的两层相互渗透的三维网络。因此，只有很小的空隙被溶剂完全占据。在 150 °C 下活化（24 小时）后，没有观察到明显的 N2 吸附现象。与钙和锶类似物 UoC-9 相比，UoC-11 没有表现出晶体海绵的行为。热分析（TGA）显示，所有溶剂分子在约 280 ° C 的温度下都会释放出来，框架在 300 ° C 以上开始分解。
{"title":"UoC‐11: An Interpenetrating MOF from Fluorinated BTB Ligands and a 1‐D Mg Based SBU","authors":"Uwe Ruschewitz, Sean S. Sebastian, Finn P. Dicke","doi":"10.1002/zaac.202400089","DOIUrl":"https://doi.org/10.1002/zaac.202400089","url":null,"abstract":"A new MOF, named UoC‐11 (UoC = University of Cologne, [Mg4(3F‐BTB)2(OAc)2(DMF)6] · DMF), based on a fluorinated BTB (4,4′,4″‐benzene‐1,3,5‐triyl‐tris‐(benzoate)) derivative and Mg cations was synthesized incorporating additional acetate anions. Its crystal structure was determined from single crystal X‐ray diffraction data (P21/c, Z = 4). It consists of one‐dimensional Mg‐SBUs (strands), interconnected perpendicularly by tritopic linkers forming a dense two‐fold interpenetrating 3D network. Thus, only very small voids are formed which are fully occupied by the solvent. After activation at 150 °C (24 hours), no meaningful N2 adsorption was observed. Compared to the Ca and Sr analogues UoC‐9, UoC‐11 does not exhibit a crystal sponge behaviour. Thermal analysis (TGA) shows a release of all solvent molecules up to ~280 °C and the decomposition of the framework starts above 300 °C.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"47 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571563","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}
Materials with tunable properties are often in the focus of materials science. Up to this point four different semiconducting materials and substitution variants have been found that are capable of switching between p‐ and n‐type conduction by a simple change in temperature. In this review, we illustrate previous findings of these pnp‐switching materials and current developments in functional implementations. While in the past decade, the scientific focus was primarily on discovering new materials that possess this intriguing switching effect, recently the first devices were successfully constructed and tested. Using the compounds, Ag18Cu3Te11Cl3 and AgCuS, that exhibit the pnp‐switching behaviour at approximately room temperature and 364 K, respectively, two single‐material diodes were developed and characterized. The approach for inducing this effect is denoted and the fundamental principles for realizing these devices are summarized.
具有可调特性的材料往往是材料科学的焦点。到目前为止，已经发现了四种不同的半导体材料和替代变体，它们能够通过简单的温度变化在 p 型和 n 型传导之间切换。在这篇综述中，我们将介绍这些 pnp 开关材料的前人研究成果以及目前在功能实现方面的发展情况。在过去的十年中，科学界的主要关注点是发现具有这种奇妙开关效应的新材料，而最近则成功构建并测试了首批器件。Ag18Cu3Te11Cl3 和 AgCuS 分别在室温和开氏 364 度左右的条件下表现出 pnp 开关行为，利用这两种化合物，我们开发出了两种单材料二极管，并对其进行了表征。文中指出了诱导这种效应的方法，并总结了实现这些器件的基本原理。
{"title":"Application Potential of pnp‑switching Semiconductors","authors":"Philipp Deng, Matthias Hoffmann, Tom Nilges","doi":"10.1002/zaac.202400066","DOIUrl":"https://doi.org/10.1002/zaac.202400066","url":null,"abstract":"Materials with tunable properties are often in the focus of materials science. Up to this point four different semiconducting materials and substitution variants have been found that are capable of switching between p‐ and n‐type conduction by a simple change in temperature. In this review, we illustrate previous findings of these pnp‐switching materials and current developments in functional implementations. While in the past decade, the scientific focus was primarily on discovering new materials that possess this intriguing switching effect, recently the first devices were successfully constructed and tested. Using the compounds, Ag18Cu3Te11Cl3 and AgCuS, that exhibit the pnp‐switching behaviour at approximately room temperature and 364 K, respectively, two single‐material diodes were developed and characterized. The approach for inducing this effect is denoted and the fundamental principles for realizing these devices are summarized.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571367","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}
Ruthenium‐catalyzed hydrosilylation of aldehydes with hydrooligosilanes is reported. Among the examined ruthenium catalysts, RuH2(CO)(PPh3)3 gave the best results. The reactions proceed with the Si–Si bonds preserved to afford the corresponding alkoxyoligosilanes in good yields. A series of aryl aldehydes with an electron‐withdrawing group is applicable, whereas those with an electron‐donating group are not suitable for the reaction. Mechanistic considerations suggest that the key points for the preservation of the Si–Si bonds are the formation of zero‐valent ruthenium species and the efficient coordination of the aldehyde to the ruthenium center prior to the oxidative addition of the Si–H bond.
{"title":"Ruthenium‐Catalyzed Hydrosilylation of Aldehydes with Hydrooligosilanes","authors":"Ken-ichiro Kanno, Yasuhiro Sunaga, Soichiro Kyushin","doi":"10.1002/zaac.202400122","DOIUrl":"https://doi.org/10.1002/zaac.202400122","url":null,"abstract":"Ruthenium‐catalyzed hydrosilylation of aldehydes with hydrooligosilanes is reported. Among the examined ruthenium catalysts, RuH2(CO)(PPh3)3 gave the best results. The reactions proceed with the Si–Si bonds preserved to afford the corresponding alkoxyoligosilanes in good yields. A series of aryl aldehydes with an electron‐withdrawing group is applicable, whereas those with an electron‐donating group are not suitable for the reaction. Mechanistic considerations suggest that the key points for the preservation of the Si–Si bonds are the formation of zero‐valent ruthenium species and the efficient coordination of the aldehyde to the ruthenium center prior to the oxidative addition of the Si–H bond.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571564","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}
Maurice Conrad, Sebastian Bette, Robert E. Dinnebier, Thomas Schleid
Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]−. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal).
{"title":"On the Thermal Dimorphy of the Strontium Perrhenate Sr[ReO4]2","authors":"Maurice Conrad, Sebastian Bette, Robert E. Dinnebier, Thomas Schleid","doi":"10.1002/zaac.202400045","DOIUrl":"https://doi.org/10.1002/zaac.202400045","url":null,"abstract":"Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> were prepared from a melt of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> ⋅ H<jats:sub>2</jats:sub>O and SrCl<jats:sub>2</jats:sub> ⋅ 6 H<jats:sub>2</jats:sub>O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO<jats:sub>4</jats:sub>]<jats:sub>3</jats:sub>‐type structure with the hexagonal space group <jats:italic>P</jats:italic>6<jats:sub>3</jats:sub>/<jats:italic>m</jats:italic> and the lattice parameters <jats:italic>a</jats:italic>=1023.81(7) pm and <jats:italic>c</jats:italic>=646.92(4) pm (<jats:italic>c</jats:italic>/<jats:italic>a</jats:italic>=0.632) for <jats:italic>Z</jats:italic>=2 in its quenchable high‐temperature form. Two crystallographically independent Sr<jats:sup>2+</jats:sup> cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re<jats:sup>7+</jats:sup> cations are found in the centers of discrete tetrahedral <jats:italic>meta</jats:italic>‐perrhenate units [ReO<jats:sub>4</jats:sub>]<jats:sup>−</jats:sup>. Temperature‐dependent <jats:italic>in‐situ</jats:italic> PXRD studies of dry powder samples of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> into the newly discovered h‐Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> (hexagonal).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"35 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506915","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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