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首页> 外文期刊>Chemistry: A European journal >Syntheses of four-membered metallacyclic complexes with nitrosylruthenium and their ring-opening upon HCl addition
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Syntheses of four-membered metallacyclic complexes with nitrosylruthenium and their ring-opening upon HCl addition

机译：四元金属环配合物与亚硝酰基钌的合成及其加HCl后的开环

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Symmetrically disubstituted bis(3-hydroxyalkynyl) complex [TpRu{C=CCPh2(OH)}(2)(NO)] (1) (Tp = BH(pyrazol-1-yl)(3)) and unsymmetrically mixed (arylalkynyl)(3-hydroxyalkynyl) congener [TpRu(C=CC6H4Me){C= CCPh2(OH)}(NO)] (2) were newly prepared. Treatment of I or 2 with p-toluenesulfonic acid monohydrate was carried out to give unusual four-membered metallacyclic complexes [TpRu{C(=C=CPh2)C(O)C(=CPh2)}(NO)] (3) and [TpRu{C=C=CPh2)- C(O)CH(C6H4Me)}(NO)] (5), respectively, as major products. Formation mechanism of 3 and 5 would involve insertion of the generated allenylidene group (Ru=C=C=CPh2) into the other Ru-C(alkynyl) bond, followed by hydration of the resulting alpha-alkynyl-allenyl fragment. With regards to the chemical reactivity of their four-membered metallacycles, treatment with aq. HCl in MeOH afforded the ring-opened one-HCl adducts, [TpRuCl{C(==CPh2)C(O)CH=CPh2}(NO)] (7) and [TpRuCl{C=C=CPh2)C(O)CH2(C6H4Me))(NO)] (8). On the other hand, the use of CH2Cl2 and THF as the reaction solvent gave another type of one-HCl adducts [TpRu{CH(C(Cl)=CPh2)C(O)C(=CPh2)}(NO)] (9 a/9 b) and [TpRu{CH(C(Cl)=CPh2)C(O)CH(C6H4Me)}(NO)] (11a/11b) as diastereomeric pairs, still retaining the four-membered ring structure. Moreover, their kinetically controlled products 9b and 11b were treated with aq. HCl to afford the ring-opened two-HCl adducts [TpRuCl{C(C(Cl)=CPh2)(H)C(O)CH=CPb2}(NO)] (10) and [TpRuCl{CH(C6H4Me)C(O)CH2(C(Cl)-Cph(2))}- (NO)] (12), respectively. In 10 and 12, each one Ru-C bond is cleaved at mutually different positions in the ring. Protonation on the carbonyl group would trigger the formation of 7-12.
机译：对称二取代的双（3-羟基炔基）络合物[TpRu {C = CCPh2（OH）}（2）（NO）]（1）（Tp = BH（吡唑-1-基）（3））和不对称混合的（芳基炔基）新制备了（3-羟基炔基）同类物[TpRu（C = CC6H4Me）{C = CCPh2（OH）}（NO）]（2）。用对甲苯磺酸一水合物处理I或2得到异常的四元金属环配合物[TpRu {C（= C = CPh2）C（O）C（= CPh2）}（NO）]（3）和[TpRu {C = C = CPh2）-C（O）CH（C6H4Me）}（NO）]分别作为主要产物（5）。 3和5的形成机理将涉及将产生的亚烯基（Ru ＝ C ＝ C ＝ CPh 2）插入另一个Ru-C（炔基）键，然后水合所得的α-炔基-烯基片段。关于其四元金属环的化学反应性，用碳酸氢钠水溶液处理。 MeOH中的HCl提供了开环的一氢氯化物加合物[TpRuCl {C（== CPh2）C（O）CH = CPh2}（NO）]（7）和[TpRuCl {C = C = CPh2）C（O ）CH2（C6H4Me））（NO）]（8）。另一方面，使用CH2Cl2和THF作为反应溶剂可得到另一种一氢氯化物加合物[TpRu {CH（C（Cl）= CPh2）C（O）C（= CPh2）}（NO）]（ 9a / 9 b）和[TpRu {CH（C（Cl）= CPh2）C（O）CH（C6H4Me）}（NO）]（11a / 11b）作为非对映体对，仍然保留了四元环结构。此外，它们的动力学控制产物9b和11b用碳酸氢钠水溶液处理。 HCl以提供开环的两个HCl加合物[TpRuCl {C（C（Cl）= CPh2）（H）C（O）CH = CPb2}（NO）]（10）和[TpRuCl {CH（C6H4Me）C （O）CH 2（C（Cl）-Cph（2））}-（NO）]（12）。在10和12中，每个Ru-C键在环中相互不同的位置断裂。羰基上的质子化将触发7-12的形成。

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