ونحن ممتنون للجمعية الألمانية للبحوث (DFG) للحصول على الدعم المالي، ونشكر الدكتور دانيال فيرنر لإجراء مناقشات مفيدة.

<ol>
	<li>Goesmann, H., Feldmann, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanoparticulate+Functional+Materials.">Nanoparticulate Functional Materials.</a> Angew. Chem. Int. Ed. 49, 1362-1395 (2010).</li><li>Purath, A., K&#246;ppe, R., Schn&#246;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=[Al7{N(SiMe3)2}6]-:+A+first+step+towards+aluminum+metal+formation+by+disproportionation.">[Al7{N(SiMe3)2}6]-: A first step towards aluminum metal formation by disproportionation.</a> Angew. Chem. Int. Ed. 38, 2926-2927 (1999).</li><li>Schn&#246;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metalloid+Al-+and+Ga-clusters:+a+novel+dimension+in+organometallic+chemistry+linking+the+molecular+and+the+solid-state+areas?.">Metalloid Al- and Ga-clusters: a novel dimension in organometallic chemistry linking the molecular and the solid-state areas?.</a> Dalton Trans. , 3131-3136 (2005).</li><li>Hu, K. -. J., Plant, S. R., Ellis, P. R., Brown, C. M., Bishop, P. T., Palmer, R. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atomic+Resolution+Observation+of+a+Size-Dependent+Change+in+the+Ripening+Modes+of+Mass-Selected+Au+Nanoclusters+Involved+in+CO+Oxidation.">Atomic Resolution Observation of a Size-Dependent Change in the Ripening Modes of Mass-Selected Au Nanoclusters Involved in CO Oxidation.</a> J. Am. Chem. Soc. 137 (48), 15161-15168 (2015).</li><li>Schno&#776;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structures+and+Properties+of+Metalloid+Al+and+Ga+Clusters+Open+Our+Eyes+to+the+Diversity+and+Complexity+of+Fundamental+Chemical+and+Physical+Processes+during+Formation+and+Dissolution+of+Metals.">Structures and Properties of Metalloid Al and Ga Clusters Open Our Eyes to the Diversity and Complexity of Fundamental Chemical and Physical Processes during Formation and Dissolution of Metals.</a> Chem. Rev. 110, 4125-4163 (2010).</li><li>Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metalloid+Cluster+Compounds+of+Germanium:+Novel+Structural+Motives+on+the+Way+to+Elemental+Germanium!.">Metalloid Cluster Compounds of Germanium: Novel Structural Motives on the Way to Elemental Germanium!.</a> New J. Chem. 34, 2079 (2010).</li><li>Schrenk, C., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metalloid+Sn+clusters:+properties+and+the+novel+synthesis+via+a+disproportionation+reaction+of+a+monohalide.">Metalloid Sn clusters: properties and the novel synthesis via a disproportionation reaction of a monohalide.</a> Rev. Inorg. Chem. 34, 93-118 (2014).</li><li>Jin, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atomically+precise+metal+nanoclusters:+stable+sizes+and+optical+properties.">Atomically precise metal nanoclusters: stable sizes and optical properties.</a> Nanoscale. 7, 1549-1565 (2015).</li><li>Schnepf, A., Dehnen, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metalloid.">Metalloid.</a> Clusters in Structure and Bonding - Clusters - Contemporary Insight in Structure and Bonding. , (2016).</li><li>Brynda, M., Herber, R., Hitchcock, P. B., Lappert, M. F., Nowik, I., Power, P. P., Protchenko, A. V., Ruzicka, A., Steiner, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Higher-Nuclearity+Group+14+Metalloid+Clusters:+[Sn9{Sn(NRR')}6].">Higher-Nuclearity Group 14 Metalloid Clusters: [Sn9{Sn(NRR')}6].</a> Angew. Chem. Int. Ed. 45, 4333-4337 (2006).</li><li>Klinkhammer, K. W., Xiong, Y., Yao, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+lead+clusters+-+from+unexpected+discovery+to+rational+synthesis.">Molecular lead clusters - from unexpected discovery to rational synthesis.</a> Angew. Chem. Int. Ed. 43, 6202-6204 (2004).</li><li>Richards, A. F., Brynda, M., Olmstead, M. M., Power, P. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+Ge5R4(R+=+CH(SiMe3)2,+C6H3-2,6-Mes2):+Germanium+Clusters+of+a+New+Structural+Type+with+Singlet+Biradical.">Characterization of Ge5R4(R = CH(SiMe3)2, C6H3-2,6-Mes2): Germanium Clusters of a New Structural Type with Singlet Biradical.</a> Organometallics. 23, 2841-2844 (2004).</li><li>Desireddy, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultrastable+silver+nanoparticles.">Ultrastable silver nanoparticles.</a> Nature. 501, 399-402 (2013).</li><li>Jadzinsky, P. D., Calero, G., Ackerson, C. J., Bushnell, D. A., Kornberg, R. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structure+of+a+Thiol+Monolayer-Protected+Gold+Nanoparticle+at+1.1+&#197;+Resolution.">Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 &#197; Resolution.</a> Science. , 430-433 (2007).</li><li>Schnepf, A., Schn&#246;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metalloid+aluminum+and+gallium+clusters:+Element+modifications+on+the+molecular+scale?.">Metalloid aluminum and gallium clusters: Element modifications on the molecular scale?.</a> Angew. Chem., Int. Ed. 41, 3532-3554 (2002).</li><li>Ecker, A., Weckert, E., Schn&#246;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+structural+characterization+of+an+Al77+cluster.">Synthesis and structural characterization of an Al77 cluster.</a> Nature. 387, 379-381 (1997).</li><li>Schnepf, A., Schn&#246;ckel, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+structure+of+a+Ga84R204-+cluster-a+link+between+metalloid+clusters+and+fullerenes?.">Synthesis and structure of a Ga84R204- cluster-a link between metalloid clusters and fullerenes?.</a> Angew. Chem. Int. Ed. 40, 712-715 (2001).</li><li>Schrenk, C., K&#246;ppe, R., Schellenberg, I., P&#246;ttgen, R., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+tin(I)bromide.+A+novel+binary+halide+for+synthetic+chemistry.">Synthesis of tin(I)bromide. A novel binary halide for synthetic chemistry.</a> Z. Anorg. Allg. Chem. 635, 1541-1548 (2009).</li><li>Schnepf, A., K&#246;ppe, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthese+von+Germanium(I)bromid.+Ein+erster+Schritt+zu+neuen+Clusterverbindungen+des+Germaniums?.">Synthese von Germanium(I)bromid. Ein erster Schritt zu neuen Clusterverbindungen des Germaniums?.</a> Z. Anorg. Allg. Chem. 628, 2914-2918 (2002).</li><li>Uhlemann, F., K&#246;ppe, R., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+metastable+Si(II)X2solutions+(X+=+F,+Cl).+A+Novel+Binary+Halide+for+Synthesis.">Synthesis of metastable Si(II)X2solutions (X = F, Cl). A Novel Binary Halide for Synthesis.</a> Z. Anorg. Allg. Chem. 640, 1658-1664 (2014).</li><li>Schenk, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Formal+Combination+of+Three+Singlet+Biradicaloid+Entities+to+a+Singlet+Hexaradicaloid+Metalloid+Ge14[Si(SiMe3)3]5Li3(THF)6Cluster.">The Formal Combination of Three Singlet Biradicaloid Entities to a Singlet Hexaradicaloid Metalloid Ge14[Si(SiMe3)3]5Li3(THF)6Cluster.</a> J. Am. Chem. Soc. 133, 2518-2524 (2011).</li><li>Schrenk, C., Schellenberg, I., P&#246;ttgen, R., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+formation+of+a+metalloid+Sn10[Si(SiMe3)3]6cluster+compound+and+its+relation+to+the+&#945;&#8596;&#946;+tin+phase+transition.">The formation of a metalloid Sn10[Si(SiMe3)3]6cluster compound and its relation to the &#945;&#8596;&#946; tin phase transition.</a> Dalton Trans. 39, 1872-1876 (2010).</li><li>Schrenk, C., Winter, F., P&#246;ttgen, R., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term={Sn10[Si(SiMe3)3]4}2-+:+A+high+reactive+metalloid+tin+cluster+with+an+open+ligand+shell+for+further+applications.">{Sn10[Si(SiMe3)3]4}2- : A high reactive metalloid tin cluster with an open ligand shell for further applications.</a> Chem. Eur. J. 21, 2992-2997 (2015).</li><li>Gutekunst, G., Brook, A. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tris(trimethylsilyl)silyllithium.3+THF:+a+stable+crystalline+silyllithium+reagent.">Tris(trimethylsilyl)silyllithium.3 THF: a stable crystalline silyllithium reagent.</a> J. Organomet. Chem. 225, 1-3 (1982).</li><li>Timms, P. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Techniques+of+Preparative+Cryochemistry.">Techniques of Preparative Cryochemistry.</a> Cryochemistry. , 61-136 (1976).</li><li>Schrenk, C., Gerke, B., P&#246;ttgen, R., Clayborne, A., Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reactions+with+a+Metalloid+Tin+Cluster+{Sn10[Si(SiMe3)3]4}2-:+Ligand+Elimination+versus+Coordination+Chemistry.">Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2-: Ligand Elimination versus Coordination Chemistry.</a> Chemistry. 21, 8222-8228 (2015).</li><li>Schnepf, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemistry+Applying+Metalloid+Tin+Clusters.">Chemistry Applying Metalloid Tin Clusters.</a> Phosphorus, Sulfur and Silicon and the Related Elements. 191, 662-664 (2016).</li></ol>

The authors do not declare any conflicts of interest.

من خلال تطبيق إعدادي تقنية شارك في التكثيف (الشكل 1) 25، والمواد رواية تقوم على الجزيئات مثل يتم الحصول SnBr. ويرجع ذلك إلى مرونة عالية في درجة الحرارة والضغط، والمعادن، والغاز على رد الفعل، مجموعة كبيرة ومتنوعة من الحلول متبدل الاستقرار من أنواع رد الفعل ...

بسبب التقدم الذي أحرز مؤخرا في مجال تكنولوجيا النانو، ومجموعة حجم النانو بين الجزيئات والحالة الصلبة أصبحت أكثر وأكثر أهمية، ويشكل محورا لمختلف الجهود البحثية 1. بحث مع مركبات nanoscaled هو خصوصا من الفائدة للمعادن أو semimetals، كما تأخذ تغييرات جذرية في أثناء التحول من الأنواع الجزيئية الصغيرة (على سبيل المثال، أكاسيد، الهاليدات: غير الموصلة، على سبيل المثال، AlCl 3، AuCl 3، الجغرافية 2، الخ) إلى مجموعات لافلز 2 من الصيغ العام M ن R م (ن&gt; م؛ M = المعادن مثل القاعدة، الاتحاد الافريقي، القصدير، وما إلى ذلك؛ R = يجند مثل SC 6 H 4 -COOH، N (سايم 3) 2، وما إلى ذلك)، إلى المرحلة النهائية السائبة عنصري (المعادن: إجراء، semimetal: شبه الموصلة، على سبيل المثال، عنصر القاعدة، الاتحاد الافريقي، أو قه) 3. تركيب وcompou nanoscaled الجزيئي واضحالثاني هو التحدي نظرا لطابعها متبدل الاستقرار. العديد من الإجراءات الاصطناعية تعطي المعادن النانوية مع توزيع حجم معين 4، وهذا يعني خليط من المركبات العنقودية لافلز من مختلف الأحجام. ونتيجة لذلك، لوضع أساس لعلاقة هيكل الملكية للمواد nanoscaled، ويجب وضع إجراءات الاصطناعية للوصول محددة مركبات جزيئية nanoscaled. هذه المركبات الجزيئية محددة (مجموعات لافلز في حالة المعادن 5، 6، 7، 8) سيسلط الضوء على التعقيد والمبادئ الأساسية للكيمياء مخادعة بسيطة، مثل حل وتشكيل المعادن 9. طريق واحد الاصطناعية للوصول إلى مجموعات لافلز من مختلف المعادن يبدأ من الحد من السلائف المستقرة التي يتم تخفيض لتشكيل كتلة لافلز، ومعظمها في العائد المنخفض (على سبيل المثال، مجموعة لافلز 14 مجموعات مثل القصدير 15 </suب&gt; (DippNSiMe 3) 6 (ديب = 2،6-حقوق الملكية الفكرية 2-C 6 H 3) 10، 10 الرصاص (HYP) 6 (HYP = سي (سايم 3 3)) 11، أو قه 5 (CH (سايم 3 ) 2) 4 12). بالإضافة إلى ذلك، تم الجمع بين عدد متزايد من مجموعات لافلز المعادن العملة عن طريق الحد من السلائف في وجود يجند محاصرة مثل [حج 44 (ع-MBA) 30] (4) - (ف ماجستير في إدارة الأعمال = ف mercaptobenzoic حامض) 13 والاتحاد الافريقي 102 (ع-MBA) 44 14. بجانب الطريق الاصطناعية تطبيق dehalogenation الاختزالية، Schnöckel وآخرون. قدم طريقا الاصطناعية لمجموعة لافلز 13 مجموعات من خلال تطبيق رد فعل disproportionation من monohalides متبدل الاستقرار شديدة التفاعل من العنصر المقابل (على سبيل المثال، 3AlCl → 2AL + AlCl 3). توليفوبالتالي إجراء monohalides اللازمة عبر تقنية شارك في التكثيف التحضيرية، حيث في درجات حرارة عالية، جزيئات الغاز مرحلة ALX وGAX (X = الكلورين، برازيلي، I) تم تجميع والمحاصرين في مصفوفة من المذيبات المجمدة (الشكل 1 بعد ذلك ) 15. وبالتالي هذا الأسلوب يتيح الوصول إلى الكواشف جديدة، وفتح الطريق إلى مناطق جديدة الكيمياء (على سبيل المثال، بدءا من monohalides متبدل الاستقرار، مجموعات لافلز بأقطار في نطاق نانومتر مثل [آل 77 (N (سايم 3) 2) 20] 2 - أو [غ 84 (N (سايم 3) 2) 20] 4 - يمكن الحصول عليها) 16، 17. الطريق الاصطناعية عن طريق رد الفعل disproportionation وبالتالي الأكثر إنتاجية، مما أدى إلى مجموعات بأقطار في نطاق نانومتر. ومع ذلك، هذا الطريق الاصطناعية لا يمكن تحقيقه إلا إذا كان subhalide متبدل الاستقرار هو في متناول اليد أن ديسبروportionates في درجات حرارة منخفضة (أقل من عادة بعيدا 0 درجة مئوية). مرة أخرى، في حالة مجموعة 14، وهناك حاجة monohalides، كما dihalides subvalent MX 2 (M = قه، القصدير، الرصاص) هي مستقرة للغاية وغير متناسبة في درجات حرارة أعلى من 100 درجة مئوية. تركيب مجموعة 14 حلول monohalide متبدل الاستقرار ممكن عن طريق تقنية شارك في التكثيف التحضيرية. ومع ذلك، يتم الحصول على مجموعة 14 monohalides في درجات حرارة أعلى من ذلك بكثير فيما يتعلق monohalides مجموعة 13، والتي هي متاحة بسهولة كأنواع مرحلة الغاز في 1000 درجة مئوية. وبالتالي، يتم الحصول SnBr في أقصى عائد على 1250 درجة مئوية 18، في حين GEBR 19، وكذلك SICL 2 20، ويتم الحصول على درجات حرارة أعلى من ذلك، حتى 1600 درجة مئوية. وmonohalides و&quot;محاصر&quot; عبر تقنية شارك في التكثيف التحضيرية (الشكل 1)، مما يؤدي إلى حلول monohalide متبدل الاستقرار. وانطلاقا من هذه الحلول متبدل الاستقرار، تمكنا مؤخرا لتجميع مجموعة سو لافلز مجموعة 14 مركبات مجموعة جديدة من الجرمانيوم والقصدير، وهي [لي (THF) 2] 3 [قه 14 (HYP) 5] (HYP = سي (سايم) 3) 21، القصدير 10 (HYP) 6 22، و { [لي ([12] تاج 4) 2]} 2 [القصدير 10 (HYP) 4] 23. هنا، نقدم تركيب حل القصدير (I) الكلورين متبدل الاستقرار داخل جهاز المشارك التكثيف محلية الصنع ووصف التفاعل مع LiHyp لإعطاء الكتلة لافلز [القصدير 10 (HYP) 4] 2-1 في ارتفاع العائد.

<table><tbody><tr><td>Tin, 99.999%</td><td>ABCR</td><td>AB122397</td><td></td></tr><tr><td>Hydrogen chloride N28, 99.8%</td><td>Air Liquide</td><td>P0820S10R0A001</td><td>Toxic</td></tr><tr><td>Toluene anhydrous, 99.8%</td><td>Sigma Aldrich</td><td>244511</td><td></td></tr><tr><td>Tri-n-butylphosphine, &amp;#62;93.5%</td><td>Sigma Aldrich</td><td>90827</td><td>Toxic</td></tr><tr><td>TMEDA, &amp;#62;99.5%</td><td>Sigma Aldrich</td><td>411019</td><td></td></tr><tr><td>12-crown-4</td><td>Sigma Aldrich</td><td>194905</td><td>Toxic</td></tr><tr><td>THF anhydrous, &amp;#62;99.9%</td><td>Sigma Aldrich</td><td>401757</td><td></td></tr><tr><td>Sodium, 99.95%</td><td>Sigma Aldrich</td><td>262715</td><td></td></tr><tr><td>Benzophenone, &amp;#62;99%</td><td>Sigma Aldrich</td><td>427551</td><td></td></tr><tr><td>Differential pressure manometer</td><td>MKS</td><td>MKS Baratron 223B</td><td></td></tr><tr><td>Mass flow controller&amp;nbsp;</td><td>Bronckhorst&amp;nbsp;</td><td>Low &amp;Delta;p flow mass flow controller</td><td></td></tr><tr><td>High frequency generator</td><td>Trumpf H&amp;uuml;ttinger</td><td>TruHeat MF 5020</td><td></td></tr><tr><td>NMR spectrometer</td><td>Bruker</td><td>Bruker DRX-250</td><td></td></tr><tr><td>Glovebox</td><td>GS Systemtechnik</td><td></td><td></td></tr><tr><td>Argon 5.0</td><td>Westfalen</td><td></td><td></td></tr><tr><td>Nitrogen 4.8</td><td>Westfalen</td><td></td><td></td></tr><tr><td>Graphite</td><td>SGL</td><td></td><td></td></tr><tr><td>Quartz glass tube</td><td>Gebr. Rettberg GmbH</td><td></td><td></td></tr><tr><td>Steel transferring cannula</td><td>Rohre Ketterer</td><td></td><td></td></tr><tr><td>Balance</td><td>Kern</td><td>Kern PFB200-3</td><td></td></tr><tr><td>Oil diffusion pump</td><td>Balzers</td><td>Balzers Diff900</td><td></td></tr><tr><td>Rotary vane pump</td><td>Balzers</td><td>Balzers QK100L4D</td><td></td></tr><tr><td>Pyrometer</td><td>Sensotherm</td><td>6285</td><td></td></tr><tr><td>Schlenk tubes with glassy stopcocks</td><td>Gebr. Rettberg GmbH</td><td>J.-Young-type valve with glassy stopcock</td><td></td></tr></tbody></table>

the synthesis of [sn10(si(sime3)3)4]2- using a metastable sn(i) halide solution synthesized via a co-condensation technique

عدد تتميز جيدا مجموعات شيبه المعدن والقصدير، وتوليفها من خلال تطبيق disproportionation من هاليد متبدل الاستقرار القصدير (I) في وجود يجند تطلبا sterically، قد زادت في السنوات الأخيرة. يتم تصنيعه في متبدل الاستقرار القصدير (I) هاليد في &quot;ظروف الفضاء الخارجي&quot; عبر تقنية شارك في التكثيف التحضيرية. وبالتالي، يتم تصنيعه في subhalide في الفرن على درجة حرارة عالية، حوالي 1300 درجة مئوية، وعلى ضغط منخفض من رد الفعل من القصدير عنصر بالغاز هاليد الهيدروجين (على سبيل المثال، حمض الهيدروكلوريك). تحصر subhalide (على سبيل المثال، SnCl) ضمن مصفوفة من مذيب خامل، مثل التولوين في -196 درجة مئوية. تسخين المصفوفة الصلبة إلى -78 درجة مئوية يعطي الحل متبدل الاستقرار من subhalide. الحل subhalide متبدل الاستقرار هو رد الفعل للغاية ولكن يمكن تخزينها في -78 درجة مئوية لمدة عدة أسابيع. على تسخين الحل لدرجة حرارة الغرفة، يحدث رد فعل disproportionation، مما يؤدي إلى القصدير الأولي والمقابلةdihalide. من خلال تطبيق بروابط ضخمة مثل سي (سايم 3) 3، ومركبات وسيطة مجموعة شيبه المعدن يمكن محاصرين من قبل disproportionation الكامل لالقصدير الأولي. وبالتالي، فإن رد فعل من القصدير متبدل الاستقرار (I) حل الكلور مع لى سي (سايم 3) 3 يعطي [القصدير 10 (سي (سايم 3) 3) 4] 2 - تتشكل بلورات 1 كما سوداء في ارتفاع العائد. 1 عن طريق سلسلة رد فعل معقد بما في ذلك تغير الوضع الملح، disproportionation، وتدهور مجموعات أكبر. وعلاوة على ذلك (1)، ويمكن تحليلها عن طريق وسائل مختلفة مثل تحليل الكريستال هيكل الأشعة السينية الرنين المغناطيسي أو واحد.

يظهر مبدأ تقنية المصفوفة العزلة في الاقتران مع تقنية شارك في التكثيف التحضيرية (الشكل 1)، وكذلك الإعداد لجهاز المشارك التكثيف (الشكل 2) ومفاعل الغرافيت (الشكل 3). أرقام 4 و 5 تظهر الصور من تجميع جهاز المشارك...

Watch this Scientific Journal Video about The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique at JoVE.com

The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

وتوليف [القصدير<sub&gt; 10</sub&gt; (سي (سايم<sub&gt; 3</sub&gt;)<sub&gt; 3</sub&gt;)<sub&gt; 4</sub&gt;]<sup&gt; 2</sup<sup&gt; -</sup&gt; باستخدام متبدل الاستقرار القصدير (I) الحل هالايد تجميعي عبر تقنية المشارك التكثيف

The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a ...

the-synthesis-sn10-si-sime3-3-42-using-metastable-sn-i-halide

Research

JoVE Journal

Chemistry

The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique

8.4K Views.  University of Tübingen. The disproportionation reaction of a metastable Sn(I) chloride solution, obtained via the preparative co-condensation technique, is used for the synthesis of a metalloid tin cluster compound.

Video: The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique

Sulfate Separation by Selective Crystallization with a Bis-iminoguanidinium Ligand

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, 1,4-benzene-bis(iminoguanidinium) (BBIG), is demonstrated. The ligand is synthesized as the chloride salt (BBIG-Cl) by in situ imine condensation of terephthalaldehyde with aminoguanidinium chloride in water, followed by crystallization as the sulfate salt (BBIG-SO4). Alternatively, BBIG-Cl is synthesized ex situ in larger scale from ethanol. The sulfate separation ability of the BBIG ligand is demonstrated by selective and quantitative crystallization of sulfate from seawater. The ligand can be recycled by neutralization of BBIG-SO4 with aqueous NaOH and crystallization of the neutral bis-iminoguanidine, which can be converted back into BBIG-Cl with aqueous HCl and reused in another separation cycle. Finally, 35S-labeled sulfate and &#946; liquid scintillation counting are employed for monitoring the sulfate concentration in solution. Overall, this protocol will instruct the user in the necessary skills to synthesize a ligand, employ it in the selective crystallization of sulfate from aqueous solutions, and quantify the separation efficiency.

A protocol for in situ aqueous synthesis of a bis(iminoguanidinium) ligand and its utilization in selective separation of sulfate is presented.

فصل كبريتات التي كتبها الانتقائية تبلور مع يجند مكرر iminoguanidinium

A simple and effective method for selective sulfate separation from aqueous solutions by crystallization with a bis-guanidinium ligand, ...

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

الجمع بين الحالة الصلبة وتقنيات أساس الحل: التجميعي والتفاعلية من Chalcogenidoplumbates (الثاني أو الرابع)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

Atmospheric Pressure Fabrication of Large-Sized Single-Layer Rectangular SnSe Flakes

Tin selenide (SnSe) belongs to the family of layered metal chalcogenide materials with a buckled structure like phosphorene, and has shown potential for applications in two-dimensional nanoelectronics devices. Although many methods to synthesize SnSe nanocrystals have been developed, a simple way to fabricate large-sized single-layer SnSe flakes remains a great challenge. Herein, we show the experimental method to directly grow large-sized single-layer rectangular SnSe flakes on commonly used SiO2/Si insulating substrates using a straightforward two-step fabrication method in an atmospheric pressure quartz tube furnace system. The single-layer rectangular SnSe flakes with an average thickness of ~6.8 &#197; and lateral dimensions of about 30 &#181;m &#215; 50 &#181;m were fabricated by a combination of vapor transport deposition technique and nitrogen etching route. We characterized the morphology, microstructure, and electrical properties of the rectangular SnSe flakes and obtained excellent crystallinity and good electronic properties. This article about the two-step fabrication method can help researchers grow other similar two-dimensional, large-sized, single-layer materials using an atmospheric pressure system.

A protocol is presented demonstrating a two-step fabrication technique to grow large-sized single-layer rectangular shaped SnSe flakes on low-cost SiO2/Si dielectrics wafers in an atmospheric pressure quartz tube furnace system.

الضغط الجوي تصنيع رقائق سنسي مستطيلة طبقة واحدة كبيرة الحجم

Tin selenide (SnSe) belongs to the family of layered metal chalcogenide materials with a buckled structure like phosphorene, and has shown potential for ...

Engineering

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

توليف لكتلة الإنشاء ثيول لبلورة إطار جيرويدال معدن الكبريت انتشارية

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Synthesis of Bimetallic Pt/Sn-based Nanoparticles in Ionic Liquids

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular physico-chemical properties of ionic liquids (ILs) are exploited to control both nucleation and growth processes. The nanoparticles form colloidal sols of very high colloidal stability in the IL, which is particularly interesting in view of their use as quasi-homogeneous catalysts. Procedures for both nanoparticle extraction in conventional solvents and for nanoparticle precipitation are presented. The size, structure and composition of the synthesized nanocrystals are confirmed using inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDX). By this, we show that the nanocrystals are random-type alloy and of small (2-3 nm) size. The catalytic activity and selectivity in the hydrogenation of &#945;,&#946;-unsaturated aldehydes is tested in a semi-continuous batch-type reactor. In this context, the bimetallic Pt/Sn-based nanoparticles reveal a high selectivity towards the unsaturated alcohol.

A protocol for the synthesis of bimetallic nanoparticles in ionic liquids and the procedure of their catalytic testing in the selective hydrogenation of unsaturated aldehydes are described.

توليف لنظام المعدنين جسيمات نانوية Pt/Sn-تعتمد في السوائل الأيونية

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular ...

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared according to the methodology developed by surface organometallic chemistry (SOMC). In this framework, catalytic cycles can be determined by isolating crucial intermediates. All air-sensitive materials are handled under inert atmosphere (using gloveboxes or a Schlenk line) or high vacuum lines (HVLs, &#60;10-5 mbar). The preparation of SiO2-700 (silica dehydroxylated at 700 &#176;C) and subsequent applications (the grafting of complexes and catalytic runs) requires the use of HVLs and double-Schlenk techniques. Several well-known characterization methods are used, such as Fourier-transform infrared spectroscopy (FTIR), elemental microanalysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR), and state-of-the-art dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP-SENS). FTIR and elemental microanalysis permit scientists to establish the grafting and its stoichiometry. 1H and 13C SSNMR allows the structural determination of the hydrocarbon ligands coordination sphere. DNP SENS is an emerging powerful technique in solid characterization for the detection of poorly sensitive nuclei (15N, in our case). SiO2-700 is treated with about one equivalent of the metal precursor compared to the amount of surface silanol (0.30 mmol&#183;g-1) in pentane at room temperature. Then, volatiles are removed, and the powder samples are dried under dynamic high vacuum to afford the desired materials [(&#8801;Si-O-)Hf(&#951;2&#960;-MeNCH2)(&#951;1-NMe2)(&#951;1-HNMe2)]. After a thermal treatment under high vacuum, the grafted complex is converted into metal imido silica complex [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)]. [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] effectively promotes the metathesis of imines, using the combination of two imine substrates, N-(4-phenylbenzylidene)benzylamine, or N-(4-fluorobenzylidene)-4-fluoroaniline, with N-benzylidenetert-butylamine as substrates. A significantly lower conversion is observed with the blank runs; thus, the presence of the imido group in [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is correlated to the catalytic performance.

A new group IV metal catalyst for imine metathesis is prepared by grafting amine metal complex onto dehydroxylated silica. Surface metal fragments are characterized using FT-IR, elemental microanalysis, and solid-state NMR spectroscopy. Further dynamic nuclear polarization surface enhanced NMR spectroscopy experiments complement the determination of the coordination sphere.

Imine Metathesis بواسطة المحفزات المدعومة من السيليكا باستخدام منهجيه الكيمياء فلزي السطحية

With this protocol, a well-defined singlesite silica-supported heterogeneous catalyst [(&#8801;Si-O-)Hf(=NMe)(&#951;1-NMe2)] is designed and prepared ...

تخليق الأطر العضوية العضوية منخفضة التكافؤ من وصلات الفوسفين متعددة المواضيع

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown to be a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from those in the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on the following: 1) the judicious choice of the metal precursor, modulator, and solvent; 2) the experimental procedures, air-free techniques, and required equipment; 3) the proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier to this new subfield of MOF research and facilitate advancements toward novel catalytic materials.

تسليط الضوء على المؤلف: مناهج تجريبية لتوليف الأطر المعدنية العضوية منخفضة التكافؤ من روابط الفوسفين متعددة الموضوعات  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous catalysts.

مناهج تجريبية لتخليق الأطر المعدنية العضوية منخفضة التكافؤ من روابط الفوسفين متعددة الموضوعات

Metal-organic frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, ...

إنتاج المركبات النانوية CdSe-SnSe من جسيمات SnSe الموحدة

Solution&#45;Processed, Surface&#45;Engineered, Polycrystalline CdSe&#45;SnSe Exhibiting Low Thermal Conductivity

In recent years, solution processes have gained considerable traction as a cost-effective and scalable method to produce high-performance thermoelectric materials. The process entails a series of critical steps: synthesis, purification, thermal treatments, and consolidation, each playing a pivotal role in determining performance, stability, and reproducibility. We have noticed a need for more comprehensive details for each of the described steps in most published works. Recognizing the significance of detailed synthetic protocols, we describe here the approach used to synthesize and characterize one of the highest-performing polycrystalline p-type SnSe. In particular, we report the synthesis of SnSe particles in water and the subsequent surface treatment with CdSe molecular complexes that yields CdSe-SnSe nanocomposites upon consolidation. Moreover, the surface treatment inhibits grain growth through Zenner pinning of secondary phase CdSe nanoparticles and enhances defect formation at different length scales. The enhanced complexity in the CdSe-SnSe nanocomposite microstructure with respect to SnSe promotes phonon scattering and thereby significantly reduces the thermal conductivity. Such surface engineering provides opportunities in solution processing for introducing and controlling defects, making it possible to optimize the transport properties and attain a high thermoelectric figure of merit.

تسليط الضوء على المؤلف: تطوير حلول الطاقة باستخدام المركبات النانوية كمواد حرارية معالجة

CdSe-SnSe nanocomposites are produced by consolidating surface-engineered SnSe particles. A simple aqueous synthesis is employed to produce SnSe particles. Coating SnSe particles with CdSe molecular complexes allows for controlling grain size and increasing the number of defects present in the nanocomposite, thus lowering the thermal conductivity.

معالج بالحل ، مصمم على السطح ، متعدد الكريستالات CdSe-SnSe يظهر موصلية حرارية منخفضة

In recent years, solution processes have gained considerable traction as a cost-effective and scalable method to produce high-performance thermoelectric ...

وتوليف [القصدير

Summary

Explore More Videos

Chapters in this video

فصل كبريتات التي كتبها الانتقائية تبلور مع يجند مكرر iminoguanidinium

الجمع بين الحالة الصلبة وتقنيات أساس الحل: التجميعي والتفاعلية من Chalcogenidoplumbates (الثاني أو الرابع)

الضغط الجوي تصنيع رقائق سنسي مستطيلة طبقة واحدة كبيرة الحجم

توليف لكتلة الإنشاء ثيول لبلورة إطار جيرويدال معدن الكبريت انتشارية

توليف لنظام المعدنين جسيمات نانوية Pt/Sn-تعتمد في السوائل الأيونية

Imine Metathesis بواسطة المحفزات المدعومة من السيليكا باستخدام منهجيه الكيمياء فلزي السطحية

مناهج تجريبية لتخليق الأطر المعدنية العضوية منخفضة التكافؤ من روابط الفوسفين متعددة الموضوعات

مناهج تجريبية لتخليق الأطر المعدنية العضوية منخفضة التكافؤ من روابط الفوسفين متعددة الموضوعات

مناهج تجريبية لتخليق الأطر المعدنية العضوية منخفضة التكافؤ من روابط الفوسفين متعددة الموضوعات

معالج بالحل ، مصمم على السطح ، متعدد الكريستالات CdSe-SnSe يظهر موصلية حرارية منخفضة