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Reactivity of phosphaalkyne tBuCP toward a Ga‐functionalized germylene 膦炔类 tBuCP 与镓官能化胚芽烯的反应活性
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-12 DOI: 10.1002/zaac.202400116
Xiaofei Sun, Peter Werner Roesky
{"title":"Reactivity of phosphaalkyne tBuCP toward a Ga‐functionalized germylene","authors":"Xiaofei Sun, Peter Werner Roesky","doi":"10.1002/zaac.202400116","DOIUrl":"https://doi.org/10.1002/zaac.202400116","url":null,"abstract":"Phosphaalkynes are the heavier congener of nitriles which feature a polarized Cδ−≡Pδ+ triple bond. Since the isolation of the first phosphaalkyne in 1981, these compounds have become important ligands for transition metals and valuable building blocks in synthetic chemistry. The reported reactivity with germylenes is rare, to expand this chemistry, we studied the reactivity of the recently developed gallium‐substituted germylene 1 ([LPhGe–Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6‐iPr2C6H3NCMe}2CH]) with tBuC≡P. Already at room temperature, insertion of the phosphaalkyne into the Ga–Ge bond occurred, resulting a metal‐functionalized (Z)‐phosphaalkenyl complex [LPhGe{C(tBu)=P}–Ga(Cl)LBDI] (2). Complex 2 was characterized by single crystal X‐ray diffraction analysis and spectroscopic methods (1H, 13C{1H}, 31P{1H} NMR and IR).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141608638","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}
引用次数: 0
An N‐Heterocyclic Germylene and Stannylene with a 1,1’‐Ferrocenylene Backbone and Dimesitylboryl N‐Substituents 一种具有 1,1'-二茂铁烯骨架和二甲苯基 N-取代基的 N-杂环锗烯和链烯
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-12 DOI: 10.1002/zaac.202400111
Hannes Lukas Jacob, Jan Cramer, Robin Guthardt, Clemens Bruhn, Ulrich Siemeling
{"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}
引用次数: 0
Synthesis and characterization of NHC stabilized bis(phenylsulfanyl)stannylene NHC 稳定双（苯硫基）锡的合成与表征
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-12 DOI: 10.1002/zaac.202400119
Aynura Mammadova, Clemens Bruhn, Rudolf Pietschnig
{"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}
引用次数: 0
Binuclear Gadolinium Complex by One‐Pot Method: Structure and Magnetic Property 一锅法钆双核配合物：结构与磁性能
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-12 DOI: 10.1002/zaac.202300238
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
{"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}
引用次数: 0
Stereoselective Synthesis of α‐Azido Esters and α‐Amino Acid Derivatives via Matteson Homologation of Boronic Esters 通过硼酸酯的马特松同系物立体选择性合成 α-叠氮酯和α-氨基酸衍生物
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-11 DOI: 10.1002/zaac.202400113
Uli Kazmaier, Alexander Horn, Emanuel Papadopoulos, Thorsten Kinsinger, Jennifer Greve, Etienne Bickel, Stavroula Pachoula
{"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}
引用次数: 0
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 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 的合成
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-11 DOI: 10.1002/zaac.202400115
Koichi Sato, Takahiro Sasamori
{"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}
引用次数: 0
UoC‐11: An Interpenetrating MOF from Fluorinated BTB Ligands and a 1‐D Mg Based SBU UoC-11：氟化 BTB 配体与一维镁基 SBU 的互穿 MOF
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-09 DOI: 10.1002/zaac.202400089
Uwe Ruschewitz, Sean S. Sebastian, Finn P. Dicke
{"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}
引用次数: 0
Application Potential of pnp‑switching Semiconductors pnp 开关半导体的应用潜力
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-08 DOI: 10.1002/zaac.202400066
Philipp Deng, Matthias Hoffmann, Tom Nilges
{"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}
引用次数: 0
Front Cover: (Z. Anorg. Allg. Chem. 11‐12/2024) 封面： (Z. Anorg. Allg. Chem. 11-12/2024)
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-06 DOI: 10.1002/zaac.202481101
{"title":"Front Cover: (Z. Anorg. Allg. Chem. 11‐12/2024)","authors":"","doi":"10.1002/zaac.202481101","DOIUrl":"https://doi.org/10.1002/zaac.202481101","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"51 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571565","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}
引用次数: 0
Ruthenium‐Catalyzed Hydrosilylation of Aldehydes with Hydrooligosilanes 钌催化的氢寡硅烷醛氢硅烷化反应
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-06 DOI: 10.1002/zaac.202400122
Ken-ichiro Kanno, Yasuhiro Sunaga, Soichiro Kyushin
{"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}
引用次数: 0
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