Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: Addition vs. substitution

Chernyshev A.N.; Bokach N.A.; Gushchin P.V.; Haukka M.; Kukushkin V.Y.

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Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: Addition vs. substitution

机译：铂（iv）结合的腈与硝基硝基苯胺异构体的反应：加成与取代

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The platinum(iv) complex trans-[PtCl _4(EtCN) _2] reacts smoothly and under mild conditions with isomeric o-, m- and p-nitroanilines (NAs) yielding two different types of products depending on the NA isomer, viz. the nitroaniline complexes cis/trans-[PtCl _4(NA) _2] (cis/trans-1-3) and the amidine species trans-[PtCl _4{NHC(Et)NHC _6H _4NO _2-m}(EtCN)] (4), trans-[PtCl _4{NHC(Et)NHC _6H _4NO _2-m} _2] (5) and trans-[PtCl _4{NHC(Et)NHC _6H _4NO _2-p}(EtCN)] (6). Complexes 4 and 5 undergo cyclometalation, furnishing mer-[PtCl _3{NHC(Et)NHC _6H _3NO _2-m}(EtCN)] (7) and mer-[PtCl _3{NHC(Et)NHC _6H _4NO _2-m}{NHC(Et)NHC _6H _3NO _2-m}] (8), respectively. Moreover, 8 both in the solid state and in solution undergoes the second step of the cyclometalation, generating [PtCl _2{NHC(Et)NHC _6H _3NO _2-m} _2] (9). In 4, the nitrile ligand is highly reactive toward nucleophilic addition and it undergoes facile hydration accompanied by the elimination of the nitrile, thus producing cis-[PtCl _4(NH _2C _6H _4NO _2-m){NHC(OH)Et}] (10), or methanol addition providing trans-[PtCl _4{NHC(Et)NHC _6H _4NO _2-m}{NHC(Et)OMe}] (11). All compounds, besides 9, were characterized by C, H, and N elemental analyses, high-resolution ESI-MS, IR, ~1H and ~13C{ ~1H} NMR spectroscopic techniques. Complex 9, which was not isolated as a pure compound, was identified in the reaction mixture by ESI-MS and ~1H and ~13C{ ~1H} NMR spectroscopies. Complexes trans-1, trans-2, 4, 5, 6, 8, 10, and 11 were additionally studied by X-ray diffraction.

机译：铂（iv）复杂的反式-[PtCl _4（EtCN）_2]在温和条件下与邻，间和对硝基苯胺异构体（NAs）平稳反应，生成两种不同类型的产物，具体取决于NA异构体，即。硝基苯胺配合物顺/反-[PtCl _4（NA）_2]（顺/反-1-3）和am类物质反-[PtCl _4 {NHC（Et）NHC _6H _4NO _2-m}（EtCN）]] 4），反式[PtCl _4 {NHC（Et）NHC _6H _4NO _2-m} _2]（5）和反式[PtCl _4 {NHC（Et）NHC _6H _4NO _2-p}（EtCN）]（6）。配合物4和5进行环金属化，得到mer- [PtCl _3 {NHC（Et）NHC _6H _3NO _2-m}（EtCN）]（7）和mer- [PtCl _3 {NHC（Et）NHC _6H _4NO _2-m} {NHC（Et）NHC _6H _3NO _2-m}]（8）。此外，固态和溶液中的8均经历了环金属化的第二步，生成了[PtCl _2 {NHC（Et）NHC _6H _3NO _2-m} _2]（9）。在第4种方法中，腈配体对亲核加成具有高反应性，并且它易于水合并消除腈，从而产生顺式[PtCl _4（NH _2C _6H _4NO _2-m）{NHC（OH）Et}]（ 10），或加甲醇以提供反-[PtCl _4 {NHC（Et）NHC _6H _4NO _2-m} {NHC（Et）OMe}]（11）。除9外，所有化合物均通过C，H和N元素分析，高分辨率ESI-MS，IR，〜1H和〜13C {〜1H} NMR光谱技术表征。通过ESI-MS以及〜1H和〜13C {〜1H} NMR光谱法在反应混合物中鉴定出未分离为纯化合物的配合物9。通过X射线衍射另外研究了复合物trans-1，trans-2、4、5、6、8、10和11。

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《Dalton transactions: An international journal of inorganic chemistry》 |2012年第41期|共8页
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Chernyshev A.N.; Bokach N.A.; Gushchin P.V.; Haukka M.; Kukushkin V.Y.;
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1. Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: Addition vs. substitution [J] . Chernyshev A.N., Bokach N.A., Gushchin P.V., Dalton transactions: An international journal of inorganic chemistry . 2012,第41期

机译：铂（iv）结合的腈与硝基硝基苯胺异构体的反应：加成与取代
2. Concentration dependent switch from addition to substitution in the reaction between salicylaldoxime and a nitrile platinum(IV) complex [J] . Bokach NA., Haukka M., Pombeiro AJL., Inorganica Chimica Acta . 2002,第0期

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3. Iminoacylation 2. Addition of alkylated hydroxylamines via oxygen to platinum(IV)-bound nitriles [J] . Gabriele Wanger, Armando J. L. Pombeiro, Yuri N. Kukushkin, Inorganica Chimica Acta . 1999,第2期

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4. Synthesis of Substituted 2,2'-Bipyridines by Cobalt-Catalyzed Cycloaddition Reactions of Nitriles and 1,6-Diynes with Exclusive Regioselectivity [C] . Taichi Ito, Avijit Goswami, Kazuhiko Ohtaki Symposium on Organometallic Chemistry . 2007

机译：用腈钴催化的环加成反应合成腈和1,6-迪杨的钴催化的循环加油反应
5. Probing the influence of the Tp' ligand on reactions of platinum(II) and platinum(IV). [D] . Engelman, Kristi L. 2010

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6. Transformation of Tri-Titanium(IV)-Substituted α-Keggin Polyoxometalate (POM) into Tetra-Titanium(IV)-Substituted POMs : Reaction Products of Titanium(IV) Sulfate with the Dimeric Keggin POM Precursor under Acidic Conditions [O] . Yuki Mouri, Yoshitaka Sakai, Yoshitaka Kobayashi, 2010

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7. Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp2)-I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1, 4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes [O] . -1

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8. Mechanism and Stereochemistry for Nucleophilic Attack at Carbon of Platinum (IV) Alkyls: Model Reactions for Hydrocarbon Oxidation with Aqueous Platinum Chlorides. [R] . Luinstra, G. A., Labinger, J. A., Bercaw, J. E. 1992

机译：铂（IV）烷基碳亲核攻击的机理和立体化学：与氯化铂水溶液的烃氧化模型反应。

Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: Addition vs. substitution

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