这项工作是由最高人民检察院1708 GT感谢的框架内利奥波尔迪纳国立Akademie的德学问的博士后奖学金内德意志研究联合会（DFG）的支持。

注意:化学品时，一定要小心谨慎。应用共同安全预防措施，包括手套，护目镜的适当利用，并且在任何时候都白大褂。特别是，要知道，含重元素，以及它们的元素来源的所有讨论的化合物，是高毒性的。 1,2-二氨基乙烷是一种腐蚀性液体。碱金属和三元的固态产品可能与空气和水分pyrophorically反应。 注意:所有的操作都采用在空气和外部湿气的严格排除标准Schlenk或手套箱技术在氩气氛中进行。含重元素金属化物种或前体的固体或溶液通过包裹用铝箔各自的容器用于抑制光诱导分解的存储的光的排斥下。 1，溶剂和溶液的制备<ol><li>加入1升新鲜购买1,2-diaminoethane至25g氢化钙2并搅拌过夜。回流（T B = 116℃），直到没有H 2的情况下（大约12小时）。 <ol><li>蒸馏在环境压力。 </li></ol></li><li> 1升氧杂环戊烷（THF）中添加至10克的NaK合金并搅拌过夜。返流（T B = 66°C）至少12小时。蒸馏在环境压力。 </li><li>加入150毫克的[Rh（PPH 3）3氯]的10毫升THF中作出的[Rh（PPH 3）3氯]的饱和溶液。在室温（RT）和滤液与低孔隙率的惰性气体过滤器的玻璃料搅拌过夜。 </li></ol> 2.高温固态反应<ol><li> 的PbSe合成2- <ol><li>将3.81克元素硒的硼硅酸盐安瓿并在上面添加元素铅5克。直到熔体的光学均匀性达到（约10分钟）用氧/甲烷燃烧器加热。用软木塞轻轻环敲安瓿整个合成分离从安瓿壁，然后将回落到反应混合物升华硒。 </li><li>允许安瓿冷却至室温。打破用杵安瓿在研钵和手动移除安瓿的所有剩余的碎片。杵粗硒化铅2淋漓尽致。 </li></ol></li><li> K 2的PbSe 2的合成 <ol><li>将0.95克元素钾和厚壁硼硅安瓿5克元素铅。慢慢地用氧/甲烷燃烧器增加热量，直到熔体的光学均匀性达到（约20分钟）。 </li><li>仔细1.9克元素硒粒料添加到熔融合金。一旦完全加入，提高温度，直至反应混合物发出明亮的黄色/白色辐射（约10分钟）并保持温度10分钟。降低反应温度，如果稍微辐射颜色将变为纯，亮白色（TE的温度接近安瓿的熔点）。 </li><li>使反应混合物冷却至室温。打破安瓿并手动删除安瓿的所有剩余的碎片和元素铅轩辕。杵粗K 2硒化铅2淋漓尽致。 </li></ol></li></ol> 3. 在原位还原<ol><li> 中的溶液的合成〔K（18-冠-6）] 2 [铅2硒3] <ol><li>放置2克的PbSe 2，3.1克18-冠-6，250毫升1,2-二氨基乙烷，并在一个圆底的 N 2 -flask上的搅拌盘的大型搅拌棒。在室温下搅拌严格，慢慢地加入0.45克元素的K. </li><li>在RT搅拌过夜，并筛选具有低孔隙率的惰性气体过滤玻璃料的溶液（孔径:D3，16-40微米或D 4，10-16微米）。 </li></ol></li></ol> 4.溶剂热反应<ol><li> K 4 [的PbSe 4]的合成＆＃183;恩·NH 3 <ol><li>放置0.5克K 2的PbSe 2和2mL 1,2-二氨基乙烷的在10毫升的小玻璃瓶中在标准的不锈钢高压釜15mL的聚四氟乙烯瓶中。紧紧关闭高压釜，并将其在烘箱中加热至150℃5天。 </li><li>关掉烤箱，并搁置1天慢慢冷却至室温。反应混合物转移到paratone石油和手动选择K 4 [硒化铅4]的晶体·恩·NH 3在15-40X倍的标准光学显微镜下。 </li></ol></li></ol> 5.无分层<ol><li> [（RhPPh 3）6（μ3 -Se）8]·0.5en的合成 <ol><li>放置10毫升的THF〔K（18-冠-6）] 2 [铅2硒3]在一个50毫升烧瓶中，添加饱和溶液的10毫升的[Rh（PPH 3）3氯]的溶液，并搅拌过夜。 </li><li>费尔之三与低孔隙率的惰性气体过滤玻璃料的反应溶液，并在24小时慢慢除去在动态真空下除去溶剂。粗反应产物转移到paratone油和15-40X倍率手动选择标准光学显微镜下[（RhPPh 3）6（μ3 -Se）8]·0.5en的晶体。 </li></ol></li><li> 合成{[K（18-冠-6）〕 - 〔K（烯）2] K的[Rh 3（CN）2（PPH 3）4（μ3 -Se）2（μ-的PbSe）]} 2· 1.3en <ol><li>放置10毫升的溶液〔K（18-冠-6）] 2 [铅2硒3]在Schlenk管和小心地用10毫升的饱和溶液的[Rh（PPH 3）3氯]在层它THF。完全覆盖Schlenk管中铝箔和离开它不受干扰4周。 </li><li>转移所产生的固体进入paratone油和李下快速选择单晶GHT显微镜。 </li></ol></li></ol> 6.解决方案和化合物的分析<ol><li>放置50毫克的"K 2的PbSe 2"上的丙烯酸类玻璃样品载体（化合物与元素硅反应），并用胶带覆盖。将其放置在环境条件下，在粉末X射线衍射装置（PXRD）和1小时23内记录的衍射数据。 </li><li>放置的溶液0.6毫升〔K（18-冠-6）] 2 [铅2硒3]核磁共振（NMR）管并彻底密封后者用保护胶带。迅速转移入核磁共振探测并记录77 Se和205铅NMR至少有2000和5000的脉冲，分别为25。 </li><li>在光学显微镜下选择单个晶体和它安装在衍射仪的测角头。具有高冗余测量它能够充分吸收校正23-33。 </li><li>执行simultaneo的电子和几何结构的我们优化的[Rh 3（CN）2（PPH 3）4（μ3硒）2（μPbSe）3 - 。与默认半径的增加了10％，占电荷补偿28施加导体状筛选模型（COSMO）。 <ol><li>计算振动频率，以保证精力充沛的最低28。 </li><li>执行马利肯和/或自然键轨道（NBO）基于密度泛函理论（DFT）波函数来获得原子电荷28分析。 </li><li>计算在轨道贡献的"松弛"和一个原结构）的完整的群集，b）该CO /自由的PbSe群集，和c）该CO /的PbSe配体，结果28进行比较。 </li></ol></li></ol>

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Chem. 640 (14), 2684-2700 (2014).</li><li>Thiele, G., Lichtenberger, N., Tonner, R., 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=Syntheses,+Structures+and+Electronic+Properties+of+a+New+Series+of+Tellurides+of+the+Type+[Sequestrated+Cation]2[Tex]+(x+=+1-4).">Syntheses, Structures and Electronic Properties of a New Series of Tellurides of the Type [Sequestrated Cation]2[Tex] (x = 1-4).</a> Z. Anorg. Allg. Chem. 639 (15), 2809-2815 (2013).</li></ol>

The authors have nothing to disclose.

经典的高温的结合，以基于溶液的方法的固态反应允许用于不能仅通过这些途径中的一个来合成的新化合物的产生和分离。尽管在大多数情况下，该中间物质的清晰识别和充分表征是难以或基本上不可能的，一般的想法是直截了当的并且可以应用于各种元素的组合。此外，对于一个具体的化合物的生成的实际的合成条件是相当灵活，并且进一步离子物质和/或不同的所涉及的元件的相对比例的存在影响产量，而不是形成本身。 K 4 [的PbSe 4]的合成·2en·NH 3，23例如，必须通过从标称组成的相位开始了"K 2的PbSe 2"为最高一愕的成就进行LDS，而在较低的产率于使用其它相的得到相同的化合物，如"KPbSe"，"K 4的PbSe 4，"或"K 2的PbSe 4"。此外，技术铅，其包含Sb的高达30％的利用率，得到相同的产物，我们惊奇的是，在比与前面提到的相甚至更好的产率。这表明一个反应机理涉及的Sb 3+ /锑5+的氧化还原步骤-与标称组成的"K 4铅点¯x锑1-X硒4"存在，例如，在相-作为用于生成一个牺牲氧化剂"铅4+"。这同样适用于mercurates，thallates和bismuthates的产生:的"K 2的PbSe 2"与HgSO 4的溶剂热反应得到的 K 2汞柱2硒3一样，的" 的K×汞柱ý硒z"的溶剂热萃取（ wher前≥y和z≤2Y; K 2汞柱2硒3是主要的反应产物）。再次，在这种溶剂热的大多数情况下"提取"，K 2汞柱2硒3可与元素比例得到的不太远固态聚变反应的名义产品。取决于各自的量，K 2汞柱3硒4，K 2硒（X = 1.3），HgSe和元素汞作为副产物在相应产率获得。 显然，这是必要的，以提供预成型multinary阶段，如从K 4 [HgSe 3]的生成推断·H 2 O 29，其从K 2 Se和HgSO 4·nH的2 O尝试来合成此合成从名义组成的一个阶段"K 4 HgSe 3"，与溶剂内变化的水分含量化合物失败。只要上述mercurates，K 2汞柱2硒3和K 2汞柱3硒4，分别代替获得。反之，K 2汞柱2硒3也至今无法从K 2 Se和HgSO 4或HgSe开始了溶剂热反应得到。 在对比关于元素比的合成的上述灵活性，溶剂或改变加入不同的溶剂的痕量对反应产物产生很大的影响。而N，N-二甲基甲酰胺缓慢分解成CO和HNME 2，慢慢增加混合物的碱性，或形式甲酸根离子，这与结晶帮助，伯胺或者倾向于以原位形成氨或坐标以各种方式中的金属离子如在[Ba（上三烯）2] 2+（三烯= 2,2&#39;- diaminodiethylamine）或[（PREN）3铕（テ3）2 Eu（上PREN）3]（PREN = 1,3-二氨基丙烷）30。痕量的水可以充当晶体溶剂，影响酸度和溶液的碱度和/或作为通过氢键模板。 对这些金属化一种不同的做法是在原位还原的途径。正式硫属富硫族化物或硫属元素中的金属硫族化合物的存在下与胺元素碱金属处理。如公知的用于在液体氨碱金属的溶液，碱金属的胺溶液具有高的还原电位。因此，该硫属元素被还原，形成可溶性硫属化物，可以与金属硫属化合物进一步反应，得到硫属化合物。但是，金属硫族化物内的金属的形式氧化态，通常不受影响。从而，可以通过此合成方法25中获得了大量的各种金属化物物种。此外，伯胺的应用，苏CH作为1,2-二氨基乙烷，产生可以存储在RT稳定的碱金属溶液（铯的异常，并在较小程度上，铷，这导致胺的瞬时降低）。此外，不同于在液氨反应，在胺反应不必在低温下进行。如所预期的，碲的还原反应通常进行较硒的快得多。另外，碲化物种的胺的溶解度通过一个数量级，通常提高。然而，所得到的telluridometalate化合物通常是对空气，水分极为敏感，以及 - 根据中心金属离子 - 也被曝光。 <img alt="图5" src="/files/ftp_upload/54789/54789fig5.jpg" /> 图5:合成方法的总结。从固态反应，起步反应途径来生成溶胶的金属化品种vothermal反应或在原位还原和由离子热反应或基于溶液的技术的装置的金属化物种的后续衍生化。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54789/54789fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 每个单独的反应的办法在图5具有固有局限性描绘。固态反应通常产生热力学产物，并且由于几乎不为三元化合物的任何相图进行了研究，所述化学计量有经由一个受过教育的试错法来进行研究。 原位反应不允许中心金属的不寻常的高氧化态（如Pb + IV），和溶剂被限制为伯胺。在离子液体中的转化反应需要从纯离析物开始，反应产物的确切性质目前还不能有预料到的。这也适用于在溶液中报道的反应，其另外的产率低，从而使随后的反应研究以及物理调查繁琐。 然而，除了可能被识别，到目前为止隔离（参见图5中的合成方法的总结）所有的金属化的化合物，一个巨大的各种polychalcogenides已经检测和隔离31,32。这些调查迄今已被忽视的，尽管它们具有吸引人的特性，也可以通过经由高收率和纯度的原位方法的直接的方法合成。与此相反，对于溶剂热反应途径，没有一般模式观察所得金属化的类型。既没有溶剂和温度的确切影响迄今阐明。预测模型，然而，似乎是这种多功能类材料合成的最终目标。

金属硫属化物，如SNSE或的CuInSe，是具有广泛的应用，例如通用的材料，如半导体，热电，或非线性光学材料1-6。类似的元素的组合物硫属化合物中发现的，其中所述金属处于正式正氧化态和由负（聚）硫属化物配体配位，以产生一个总的阴离子物质。不同于上述材料，例如金属化物附加地包括反离子，其是公由阴离子子隔开。典型的阳离子是（溶剂化）碱金属或碱土金属，铵或鏻离子。大多数情况下，与chalcogenidometalate阴离子例如盐具有的物理性质是类似于亲本的二元或三元化合物，如类似的带隙或光和半导电性能。然而，由于各元素内c的广泛范围的可能的阴离子结构ombination，从通过股线和互联的阴离子为扩展三维框架片分离的分子种类，各种性质的一个更精细的调谐，可以实现最终瞄准具有所需性质的化合物的设计合成。内降维的概念，它已经表明，每式单元，伴随经由二维和一维从3D还原以0D阴离子结构（0D表示分子物质）的反离子的相对增加，降低所观察到的带隙7。此外，通过不同的（或混合物）硫属化物的配位体的使用，它甚至有可能达到的带隙8,9-超细调整。 除了这些实际应用的有远见relevancies，硫属化合物仍在研究对基本理解，诸如用于新颖的阴离子结构类型的产生或发现和INTE一个不寻常的粘接rpretation，以及它们的前所未有的属性。而较轻的同源物（ 即，oxidometalates，通常被称为oxometalates）已被广泛研究，尤其是用于潜在催化应用，较重的硫属化合物是少得多的探讨。 我们自己的兴趣一直集中在合成，属性和chalcogenidotetrelates进一步反应（即硅酸盐较重的同源物）10,11。有各种各样这样的化合物，从水稳定且可溶的二元阴离子，如[SNTE 4] 4-阴离子12;有机的，官能化和multinary簇化合物，如{[铱3（鳕鱼）3（μ3 -S）2]（μ3 -S）的SnCl} 2（COD =环辛-1,5-二烯）13。我们最近的研究处理chalcogenidoplumbates，用铅作为中心金属在OM（S）。在与重原子的惰性，对理念，解决6S轨道的稳定，由于相对论效应，率先在正规+ II氧化态所观察的通常。像的PbO 2的例外是强氧化剂，和较重的铅（IV）的硫属化物，"PBCH 2，"没有被发现的日期14。这同样适用于所述chalcogenidoplumbate（Ⅳ）的阴离子，其中只有[的PbO 4] 4 -已经报道15直到最近（见下文）。 除了一个不同的小组结构调查oxidoplumbates（Ⅱ，Ⅳ），已经出现了chalcogenidoplumbates（Ⅱ），即只有几个例子[的PbTe 3] 4 - ，具有三角锥型阴离子16;和[铅2 CH 3] 2 - ，其中CH = Se或Te，具有三角双锥阴离子17。这些是由也被应用的路线合成为Zintl的产生离子18。经在高温下的元素融合制备multinary金属间相，随后在螯合剂的存在下提取由溶剂，得到在（单）晶体形式的所需产物。在的情况下，[铅2 CH 3] 2 -的阴离子，例如，标称成分的相位"KPbCh"已经在4,7,13,16存在下1,2-二氨基乙烷（烯）萃取，21,24六氧-1,10-二氮杂双环[8.8.8]二十六烷（双环[2.2.2]隐窝）。的穴状配体是必要既用于在在[KP [2.2.2]隐窝}有效阳离子半径+络合物抗衡离子的增加结晶，以更好地匹配阴离子大小，而对于正电荷的屏蔽，抑制电子回-donation从在溶液中的阴离子。相比于当封装的阳离子这样的盐通常揭示结晶高的倾向，因此，相当不错的收益相应的盐，而不封存剂。然而，相当麻烦的合成或穴状的高房价阻止这种方法的过度扩展。 与此相反，K 4 [的PbTe 3]·2en经由在溶液原位还原合成，如已经早在1891年用于著名铅9 4的产生-阴离子19,20。对于后者，元素碱金属加入到铅悬浮在液态氨在低温下，而对于telluridoplumbate，标称组合物"的PbTe 2"的合金，在室温下通过加入元素的钾降低，一次。 我们对这种金属化物种第一种方法将本文中所呈现的这两个途径的组合。这里，固态合成之后是在溶液中廉价螯合剂阿格纳的存在或减少TS，如1,4,7,10,13,16- hexaoxacyclooctadecane（18-冠-6），或通过减少与由溶剂本身螯合碱金属，而不需要额外的多价螯合剂，类似合成的[娜4（EN）7] [9锡] 21。我们的第二种方法也开始与高温合成，但它接着将得到的相的溶剂热提取（ 即，提取在升高的温度和压力下）22。在下文中，我们将提出两个合成方法和一些我们最近在这些反应途径的应用的结果。

<table border="0" cellpadding="0" cellspacing="0" width="655">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Ethan-1,2-diamine</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td style="width:136px;">E26266-2.5L</td>
			<td style="width:191px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Calcium hydride</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>213268-100G</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Tetrahydrofuran</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>401757-1L</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Sodium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>71172-1KG</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Potassium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>244864-50G</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Tris-triphenylphosphine rhodium chloride</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>199982-5G</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:247px;">Lead</td>
			<td style="width:81px;">Acros</td>
			<td align="right">222625000</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Selenium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>209643-50G</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:247px;">18-crown-6</td>
			<td style="width:81px;">Acros</td>
			<td align="right">181561000</td>
			<td></td>
		</tr>
	</tbody>
</table>

combining solid-state and solution-based techniques: synthesis and reactivity of chalcogenidoplumbates(ii or iv)

"PBCH 2"（CH =硒，碲）的相位从固态合成得到的（ 即 ，通过在石英玻璃安瓿在惰性条件下的元件的融合）。通过在胺元素碱金属如相减，得到结晶chalcogenidoplumbate（Ⅱ）由[的PbTe 3] 2的盐-或[铅2 CH 3] 2 -阴离子，这取决于其中螯合剂为阳离子存在:冠醚，像18-冠-6，或穴状配体，如[2.2.2]隐窝。与过渡金属化合物产量（聚）硫系阴离子或过渡金属簇硫族化合物，其中包括一个具有μ-硒化铅配体（ 即 ，最重的知名CO同源物）这样的阴离子溶液的反应。 与此相反，标称组成的一相的固态合成的"K 2的PbSe 2"的元素的连续反应S和由在胺随后溶剂热处理产生第一非氧化物/卤化物无机铅（IV）的化合物: 邻 -selenidoplumbate（IV）的阴离子的盐[的PbSe 4] 4 - 。这是出乎意料的，由于铅（IV）和硒（-II）的氧化还原电位。这样的方法可以进一步应用于其它元素的组合，导致二进制[HGTE 2] 2溶液形成-或[BISE 3] 3 -的阴离子，或至K 2汞柱2硒3或K 3的大规模合成碧色3通过固态路线。 所有化合物的特征在于由单晶X射线衍射和元素分析;铅酸盐溶液可通过205 Pb和77或硒碲127核磁共振技术来研究。采用密度泛函理论方法量子化学计算使能量比较。他们还允许为分析上市的电子组态，从而，接合情况。含铑分子被发现谢夫尔型化合物显示出离域混合价，而类似telluridopalladate阴离子电子精确;与μ-硒化铅配体集群正在大力赞成对一个假设的CO模拟，符合其合成失败的尝试。正式铅（IV）中的[的PbSe 4] 4内的稳定性-阴离子主要是由于晶格内的适当稳定化。

邻 -selenidoplumbate阴离子的存在[的PbSe 4] 4 - 23（参见图1，右上）已经由单晶衍射实验，元素分析，和量子化学计算证实。晶体结构细化证实了几乎完美的四面体配位几何形状，如所预期的铅（Ⅳ）离子，而DFT计算合理化大力稳定一个 1表示，这有助于阴离子的整体稳定性（参见图1，右下角）。负离子是其钾盐的分离是可能通过阴离子本身的稳定性意外造成的，但主要是由于合理的晶体结构中纳入。这是通过阴离子类似措施合理化相比其同系物，公知的[SNTE 4] 4 </s达&gt; - 。 K 4 [的PbSe 4]·烯·NH 3表示第一无机铅（IV）的化合物不高度电负性的配体，如氧或氟原子。 <img alt="图1" src="/files/ftp_upload/54789/54789fig1.jpg" /> 图1:K 4 [的PbSe 4]。恩。 NH 3。反应途径为K 4 [的PbSe 4]的合成。恩。 的 NH 3（a）中 。的[的PbSe 4] 4表示-的阴离子，如通过用热椭圆单晶X射线衍射装置，在50％的概率来确定（b）中 。宏观外观（c）所示 。通过能量色散X射线光谱（d）该元素分析的结果。与幅度的量子化学计算结果为0.033太子港绘制（E </str翁&gt;）。图中的零件与威利 - VCH权限进行了转载。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54789/54789fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 用相同的合成方案的手段应用于K 4 [的PbSe 4]·2en·NH 3，但使用不同的元素组合，化学计量，可以得到进一步的金属化材料。例如，K 2汞柱2硒3 24是一个半及感光材料的基于三维方向相连selenidomercurate管聚阴离子子。可以在大尺度和高收率地得到的化合物。这是热电应用前景的原型，尽管非常元素的组合表现出过大的带隙，由DFT计算周期性边界的c手段证明onditions和由紫外（UV）-visible光谱。这会导致相当低的电子传导性，如实验合理化。然而，带隙可以通过合成较重同源减小，K 2汞柱2碲3（ 图2），由数个数量级这的确引起的增加的光电导。 <img alt="图2" src="/files/ftp_upload/54789/54789fig2.jpg" /> 图2:K 2汞柱2硒3。反应途径的K 2汞柱2硒图3（a）的合成。沿C型通道结构的表示（B，C）根据单晶X射线衍射，热（d）和光电子分析（E，F）。阻抗谱结果（g）和钙ulated带结构（ 小时 ）。图中的部件来自美国化学学会的权限进行了转载。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54789/54789fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 金属化物阴离子的高产率和高纯度的解决方案不仅促进其分离和充分表征25，但它们也可用于进一步反应性研究，产生，例如，分子谢夫尔型化合物，例如[（RhPPh 3）6（ μ-CH）8]（CH =硒，碲）或阴离子[钯6（μ-Te）的8] -4 - （ 图3）26,27。有趣的是，磷化氢饱和（因此，整体中性）种包括混合价的Rh 2+ /铑3+离子，通过量子化学计算的手段合理化。像C哈耶是在群集核心，由单晶衍射确定不允许对不同形式氧化态的分配结构高度离域。阴离子telluridopalladate簇，与此相反，是电子精确。加入Pd（II）离子通过一个扭曲的正方形平面协调环境，因而用于向路易斯碱性化合物进一步反应，如在催化过程有趣。 <img alt="图3" src="/files/ftp_upload/54789/54789fig3.jpg" /> 图3:分子谢夫尔型化合物。用于合成反应途径[李4（烯）10] [钯4碲8]和[（PPH 3）6的Rh 6硒8]·烯（a）中 。如由单晶X射线衍射来确定结构化表示（B，C）。图中的零件与permi转载裂变从美国化学学会。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54789/54789fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> 非常类似的反应条件，但不同的处理过程，得到具有的[Rh 3硒2]单位，采用三角双锥形状，硒在基面28的顶端位置和Rh化合物。这些单元表示可以有选择地通过加入某些抗衡离子螯合剂（ 图4）的分离不同的阴离子簇配合物的核心。的[Rh 3（PPH 3）6（μ3 -Se）2] - ，具有两个PPH 3的配位体配位的每个上的Rh（I）中的原子的，结晶作为在加入[2.2.2]隐窝其盐。使用18-冠-6代替产生所述的[Rh 3（CN）的盐2 </sub&gt;（PPH 3）4（μ3 -Se）2（μ-的PbSe）3 -的阴离子，其中只有的Rh（I）的原子中的一个带有2膦配位体，而另外两个被一个CN协调-配位体每。此外，最显着地，后两种金属原子之间的μ-的PbSe配体桥。所述的PbSe片段是第二重一氧化碳同系物和最重的1观察到的日期。量子化学计算有助于表明用CO代替的PbSe在桥接位置对应的复杂的将被否定，如硒化铅的大小和粘合性能更好地匹配簇芯的要求。在这条线，在CO气氛实验未能产生一个对应的μ-CO-桥接物种。 <img alt="图4" src="/files/ftp_upload/54789/54789fig4.jpg" /> 图4:μ-硒化铅:一个非常沉重的CO模拟。反应途径（a）和结构表示，如由为[铑3（CN）2（PPH 3）4（μ3 -Se）2（μ-的PbSe）〕3-（ 二单晶X-射线衍射测定）和[铑3（PPH 3）6（μ3 -Se）2] - （C）的阴离子。图中的零件与威利 - VCH权限进行了转载。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/54789/54789fig4large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

Watch this Scientific Journal Video about Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV at JoVE.com

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.

结合固态和基于解决方案的技术合成及Chalcogenidoplumbates的反应（II或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 ...

combining-solid-state-solution-based-techniques-synthesis-reactivity

Nanyang Technological University

Research

JoVE Journal

Chemistry

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

10.6K 次观看.  University of California, Berkeley. 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 µ-PbSe ligand. 

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

Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid phase by using combinatorial chemistry. One of the most well studied classes of peptidomimetics is peptoids. Peptoids are easy to synthesize and have been shown to be proteolysis-resistant and cell-permeable. Over the past decade, many useful protein ligands have been identified through screening of peptoid libraries. However, most of the ligands identified from peptoid libraries do not display high affinity, with rare exceptions. This may be due, in part, to the lack of chiral centers and conformational constraints in peptoid molecules. Recently, we described a new synthetic route to access peptide tertiary amides (PTAs). PTAs are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. With side chains on both &#945;-carbon and main chain nitrogen atoms, the conformation of these molecules are greatly constrained by sterical hindrance and allylic 1,3 strain. (Figure 1) Our study suggests that these PTA molecules are highly structured in solution and can be used to identify protein ligands. We believe that these molecules can be a future source of high-affinity protein ligands. Here we describe the synthetic method combining the power of both split-and-pool and sub-monomer strategies to synthesize a sample one-bead one-compound (OBOC) library of PTAs.

Peptide tertiary amides (PTAs) are a superfamily of peptidomimetics that include but are not limited to peptides, peptoids and N-methylated peptides. Here we describe a synthetic method which combines&#160;both split-and-pool and sub-monomer strategies to synthesize a one-bead one-compound library of PTAs.

分裂和池合成及肽叔酰胺图书馆表征

Peptidomimetics are great sources of protein ligands. The oligomeric nature of these compounds enables us to access large synthetic libraries on solid ...

科研

化学

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

一系列钌的合成，表征和反应<em&gt;Ñ</em&gt; -triphos<sup&gt;博士</sup&gt;配合

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

超分子胶体的合成与表征

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

X-ray Powder Diffraction in Conservation Science: Towards Routine Crystal Structure Determination of Corrosion Products on Heritage Art Objects

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder diffraction (XRPD) is presented in detail via two case studies.
The first material under investigation was sodium copper formate hydroxide oxide hydrate, Cu4Na4O(HCOO)8(OH)2&#8729;4H2O (sample 1) which forms on soda glass/copper alloy composite historic objects (e.g., enamels) in museum collections, exposed to formaldehyde and formic acid emitted from wooden storage cabinets, adhesives, etc. This degradation phenomenon has recently been characterized as &#34;glass induced metal corrosion&#34;.
For the second case study, thecotrichite, Ca3(CH3COO)3Cl(NO3)2&#8729;6H2O (sample 2), was chosen, which is an efflorescent salt forming needlelike crystallites on tiles and limestone objects which are stored in wooden cabinets and display cases. In this case, the wood acts as source for acetic acid which reacts with soluble chloride and nitrate salts from the artifact or its environment.
The knowledge of the geometrical structure helps conservation science to better understand production and decay reactions and to allow for full quantitative analysis in the frequent case of mixtures.

Modern high resolution X-ray powder diffraction (XRPD) in the laboratory is used as an efficient tool to determine crystal structures of long-known corrosion products on historic objects.

X射线粉末衍射在保护科学:迈向文物艺术品腐蚀产物的常规晶体结构测定

The crystal structure determination and refinement process of corrosion products on historic art objects using laboratory high-resolution X-ray powder ...

Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been previously demonstrated. However, the dyeing process takes a long time to complete compared to commercial hair-dyeing products. To overcome this bottleneck, pre-synthesized polymeric products of the oxidative reaction of Trametes versicolor laccase on catechin and catechol, either with or without mordant agents (e.g., FeSO4), were here employed to achieve permanent keratin hair dyeing in various colors and shades. The laccase action in acidic sodium acetate buffer led to a deep black coloration after coupling reactions between the plant phenols. The colored dye products were then desalted and concentrated with ultrafiltration. The dyes, with or without mordant agents, caused a significant increase in &#916;E values (i.e., color difference value) in gray human hair within 2.5 hours. In addition, different keratin colors and shades were induced depending upon the mordanting and pH changes. The dyed hair also exhibited a strong resistance to detergent treatments, indicating that our methods can give rise to permanent hair dyeing.&#160;Overall, our work has provided novel insight into developing eco-friendly hair-dyeing methods as alternatives to commercial toxic diamine-based dyes.

Here, we present a protocol to use pre-synthesized polymeric products derived from fungal laccase-catalyzed polymerization of plant phenols, either with or without mordant agents (e.g., FeSO4), to induce detergent-resistant keratin hair dyeing within 2.5 hours.

对于直接或媒介为基础的头发染色厂苯酚衍生的高分子染料的合成

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been ...

Measurement of Particle Size Distribution in Turbid Solutions by Dynamic Light Scattering Microscopy

A protocol for measuring polydispersity of concentrated polymer solutions using dynamic light scattering is described. Dynamic light scattering is a technique used to measure the size distribution of polymer solutions or colloidal particles. Although this technique is widely used for the assessment of polymer solutions, it is difficult to measure the particle size in concentrated solutions due to the multiple scattering effect or strong light absorption. Therefore, the concentrated solutions should be diluted before measurement. Implementation of the confocal optical component in a dynamic light scattering microscope1 helps to overcome this barrier. Using such a microscopic system, both transparent and turbid systems can be analyzed under the same experimental setup without a dilution. As a representative example, a size distribution measurement of a temperature-responsive polymer solution was performed. The sizes of the polymer chains in an aqueous solution were several tens of nanometers at a temperature below the lower critical solution temperature (LCST). In contrast, the sizes increased to more than 1.0 &#181;m when above the LCST. This result is consistent with the observation that the solution turned turbid above the LCST.

A protocol for the direct measurement of particle size distribution in concentrated solutions using dynamic light scattering microscopy is presented.

通过动态光散射显微镜混浊解决方案粒度分布的测定

A protocol for measuring polydispersity of concentrated polymer solutions using dynamic light scattering is described. Dynamic light scattering is a ...

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

We present herein the optimized synthesis of a triphosphenium bromide salt. Apart from being a versatile metathesis reagent, this unusually stable low-valent-phosphorus-containing compound acts as a useful P+ transfer agent. Unlike traditional methods employed to access low-coordinate phosphorus species which usually require pyrophoric phosphorus-containing precursors (white phosphorus, Tris(trimethylsilyl)phosphine, etc.), or harsh reducing agents (alkali metals, potassium graphite, etc.), the current approach does not involve pyrophoric or explosive reagents and can be done on large scales (&#62;20 g) in excellent yields by undergraduates with basic air-free synthetic training. The bromide counter ion is readily exchanged with other anions such as tetraphenyl borate (described herein) using typical salt metathesis reagents to obtain materials with desired properties and reactivities. The versatility of this P+ transfer approach is exemplified by the reactions of these triphosphenium precursors with an N-heterocyclic carbene and an anionic bisphosphine, each of which readily displace the neutral bisphosphine to give an NHC-stabilized phosphorus(I) cation and a phosphorus(I) containing zwitterion, respectively.

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI

The synthesis of a triphosphenium bromide salt is described and its use as a P+ transfer agent is outlined by reactions with an N-heterocyclic carbene and an anionic bisphosphine, yielding an NHC-stabilized P(I) cation and a P(I) containing zwitterion, respectively.

制备及反应性的Triphosphenium溴化物盐:磷方便稳定来源（I）

We present herein the optimized synthesis of a triphosphenium bromide salt. Apart from being a versatile metathesis reagent, this unusually stable ...

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

A rapid, direct solution-based reduction synthesis method to obtain Au, Pd, and Pt aerogels is presented.

直接溶液还原法快速合成金、钯、铂气凝胶的研究

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various ...

Synthesis and Characterization of Amphiphilic Gold Nanoparticles

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of their interactions with cell membranes, lipid bilayers, and viruses. The hydrophilic ligands make these particles colloidally stable in aqueous solutions and the combination with hydrophobic ligands creates an amphiphilic particle that can be loaded with hydrophobic drugs, fuse with the lipid membranes, and resist nonspecific protein adsorption. Many of these properties depend on nanoparticle size and the composition of the ligand shell. It is, therefore, crucial to have a reproducible synthetic method and reliable characterization techniques that allow the determination of nanoparticle properties and the ligand shell composition. Here, a one-phase chemical reduction, followed by a thorough purification to synthesize these nanoparticles with diameters below 5 nm, is presented. The ratio between the two ligands on the surface of the nanoparticle can be tuned through their stoichiometric ratio used during synthesis. We demonstrate how various routine techniques, such as transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and ultraviolet-visible (UV-Vis) spectrometry, are combined to comprehensively characterize the physicochemical parameters of the nanoparticles.

Amphiphilic gold nanoparticles can be used in many biological applications. A protocol to synthesize gold nanoparticles coated by a binary mixture of ligands and a detailed characterization of these particles is presented.

两栖金纳米粒子的合成与表征

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of ...

Hierarchical and Programmable One-Pot Oligosaccharide Synthesis

This article presents a general experimental protocol for programmable one-pot oligosaccharide synthesis and demonstrates how to use Auto-CHO software for generating potential synthetic solutions. The programmable one-pot oligosaccharide synthesis approach is designed to empower fast oligosaccharide synthesis of large amounts using thioglycoside building blocks (BBLs) with the appropriate sequential order of relative reactivity values (RRVs). Auto-CHO is a cross-platform software with a graphical user interface that provides possible synthetic solutions for programmable one-pot oligosaccharide synthesis by searching a BBL library (containing about 150 validated and &#62;50,000 virtual BBLs) with accurately predicted RRVs by support vector regression. The algorithm for hierarchical one-pot synthesis has been implemented in Auto-CHO and uses fragments generated by one-pot reactions as new BBLs. In addition, Auto-CHO allows users to give feedback for virtual BBLs to keep valuable ones for further use. One-pot synthesis of stage-specific embryonic antigen 4 (SSEA-4), which is a pluripotent human embryonic stem cell marker, is demonstrated in this work.

This protocol demonstrates how to use the Auto-CHO software for hierarchical and programmable one-pot synthesis of oligosaccharides. It also describes the general procedure for RRV determination&#160;experiments and one-pot glycosylation of SSEA-4.

分层和可编程单罐寡糖合成

This article presents a general experimental protocol for programmable one-pot oligosaccharide synthesis and demonstrates how to use Auto-CHO software for ...