Einblicke in die Chemie kurzlebiger P‐Chlorphosphanyl‐Komplexe
Einblicke in die Chemie kurzlebiger P‐Chlorphosphanyl‐Komplexe
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深入了解短寿命对氯膦酰配合物的化学性质
DOI：
10.1002/anie.201002885
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发表时间：
2010
影响因子：
--
通讯作者：
R. Streubel
中科院分区：
文献类型：
--
作者：
A. Özbolat-Schön;M. Bode;G. Schnakenburg;M. van Gastel;A. Anoop;F. Neese;R. Streubel
具有一个或多个未成对电子的主族元素化合物是近年来研究的热点。[1，2] MF Lappert埃塔尔在具有低配位磷中心的磷基自由基领域取得了根本性突破[3]。随着I型的第一个稳定衍生物（R= CH（SiMe 3）2）的合成，[4]其在结晶时二聚化（可逆）。[5]该化合物已被用作钴和铁羰基络合物中的配体。[6]最近，已经合成了II [7]和III [8]的杂原子取代的衍生物（方案1）。有趣的后续反应，涉及重排和分解过程的III已被观察到。相比之下，关于具有潜在离去基团的衍生物IV [9，10]的知识非常稀少，并且据我们所知，其配位化学是未知的。后者是特别感兴趣的，因为开壳复合物已被认为是非常有趣的目标，例如作为分子成像的造影剂。[11]我们目前对Li/Cl-膦酰络合物化学的研究[12-16]使我们发现了通过单电子氧化形成的瞬时P-氯膦酰络合物。这些瞬态复合物进行组合的交叉偶联/重排和交叉偶联/消除反应，在后一种情况下产生的第一个结构特征的衍生物的磷醌甲烷复合物。使用LDA/[12]冠-4 [12，14]将对氯膦配合物1a [17]和1 B [18]转化为对氯膦类配合物2a，B，然后在低温下用四氟硼酸三苯甲基铵处理。缓慢升温得到配合物5和6，其使用柱色谱法分离。所提出的反应途径如方案2所示，涉及在氧化时形成由三苯甲基鎓自由基和P-氯磷酰基配合物3a、B组成的自由基对。在C、P偶联反应产生络合物4a、B之后，或者随后发生H-移位以形成络合物5，或者发生HCl消除以产生络合物6。通过ESR光谱和DFT研究证实了开壳中间体3a、B的存在（见下文）。
Main-group-element compounds with one or more unpaired electrons have emerged as a fascinating research topic in recent years.[1, 2] The fundamental breakthrough in the area of phosphorus-based radicals with low-coordinate phosphorus centers [3] was achieved by MF Lappert etal. with the synthesis of the first stable derivative of type I (R= CH (SiMe3) 2),[4] which dimerizes (reversibly) upon crystallization.[5] This compound has been used as a ligand in cobalt and iron carbonyl complexes.[6] More recently, heteroatomsubstituted derivatives of II [7] and III [8] have been synthesized (Scheme 1). Interesting follow-up reactions involving rearrangement and decomposition processes of III have been observed. In contrast, knowledge about derivatives IV,[9, 10] which have potential leaving groups, is extremely scarce and, to the best of our knowledge, its coordination chemistry is unknown. The latter is of special interest, as open-shell complexes have been recognized as highly interesting targets, for example as contrast agents for molecular imaging.[11] Our current investigations of Li/Cl-phosphinidenoid complex chemistry [12–16] has led us to the discovery of transient P-chlorophosphanyl complexes formed by one-electron oxidation. These transient complexes undergo combined crosscoupling/rearrangement and cross-coupling/elimination reactions, which in the latter case yielded the first structurally characterized derivative of a phosphaquinomethane complex. P-Chlorophosphane complexes 1a [17] and 1b [18] were transformed into the P-chlorophosphinidenoid complexes 2a, b using LDA/[12] crown-4,[12, 14] and then treated with tritylium tetrafluoroborate at low temperature. Slow warmup yielded the complexes 5 and 6, which were isolated using column chromatography. The proposed reaction pathway is shown in Scheme 2 and involves the formation of a radical pair consisting of the tritylium radical and the P-chlorophosphanyl complexes 3a, b upon oxidation. After a C, P coupling reaction leading to complexes 4a, b, either a subsequent H-translocation occurs to form complex 5 or HCl elimination takes place to give complex 6. The presence of the open-shell intermediates 3a, b was confirmed by ESR spectroscopic and DFT investigations (see below).
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影响因子：
16.6
作者：
Drost, Christian;Griebel, Jan;Reinhold, Joachim
通讯作者：
Reinhold, Joachim
磷和砷的稳定二烷基和二酰胺R12M·和(R22N)2M·的合成和电子自旋共振研究
DOI：
--
发表时间：
1976
期刊：
影响因子：
--
作者：
M. Gynane;A. Hudson;M. Lappert;P. Power
通讯作者：
P. Power
瞬态膦类复合物的有力证据。
影响因子：
--
作者：
Aysel Ozbolat;Gerd von Frantzius;J. M. Pérez;M. Nieger;R. Streubel
通讯作者：
R. Streubel
1-Aza-3λ3-phospha-1-allenide 配合物的尝试合成：不寻常的 Phosphanide 配合物的结构和反应
影响因子：
2.8
作者：
Aysel Özbolat;G. V. Frantzius;E. Ionescu;S. Schneider;M. Nieger;and Peter G. Jones;R. Streubel
通讯作者：
R. Streubel
.beta.-亚甲基-DL-天冬氨酸：谷氨酸-天冬氨酸转氨酶的选择性抑制剂
DOI：
--
发表时间：
1982
期刊：
影响因子：
--
作者：
Arthur J. L. Cooper;S. Fitzpatrick;C. Kaufman;P. Dowd
通讯作者：
P. Dowd