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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Rearrangement and deoxygenation of 3,3-bis(2-pyridyl) oxaphosphirane complexes

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Rearrangement and deoxygenation of 3,3-bis(2-pyridyl) oxaphosphirane complexes

机译：3,3-双（2-吡啶基）氧杂磷杂环丙烷配合物的重排和脱氧

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The reaction of Li/Cl phosphinidenoid pentacarbonylmetal(0) complexes 2a-c (R = CH(SiMe3)(2); M = Cr, Mo, W) with bis(2-pyridyl) ketone led to overcrowded 3,3-bis(2-pyridyl) oxaphosphirane complexes 3a-c. On heating (pyridine at 95 degrees C or THF at 60 degrees C) 3c was transformed into complex 4c which had a novel heterobicyclic P-ligand. In the case of the P-Cp* derivative 2d the reaction led to a mixture of oxaphosphirane complex 3d and complex 4d, whereas only the novel heterobicyclic complex 4e was formed in the case of the P-CPh3 substituted complex 2e. Single-crystal X-ray analysis of 4e confirmed the structure of the new ligand as an isomer of the oxaphosphirane which rearranged under loss of aromaticity of one pyridyl substituent. DFT calculations on the P-Me model derivative 3f revealed that, despite the easier CO bond cleavage in oxaphosphirane complex 3, only the P-C bond cleavage intermediate 6 enables kinetically favoured P-N ring closure to give the bicyclic P-ligand in 4. Preliminary studies demonstrated that complex 3c reacts with an in situ generated Ti(III) complex to give the phosphaalkene complex 10c, the hetero-dinuclear complex 10c.ZnCl2 and the P, N-chelate complex 11c.

机译：Li / Cl膦亚基五羰基金属（0）配合物2a-c（R = CH（SiMe3）（2）; M = Cr，Mo，W）与双（2-吡啶基）酮的反应导致3,3-bis过度拥挤（2-吡啶基）氧杂膦酸酯络合物3a-c。在加热下（95℃的吡啶或60℃的THF），将3c转化为具有新型杂环双环P-配体的配合物4c。在P-Cp *衍生物2d的情况下，反应导致氧杂磷杂环丙烷配合物3d和配合物4d的混合物，而在P-CPh 3取代的配合物2e的情况下仅形成新型的杂环双环配合物4e。对4e的单晶X射线分析证实了作为氧杂膦酸酯的异构体的新配体的结构，其在一个吡啶基取代基的芳香性损失下重新排列。 DFT对P-Me模型衍生物3f的计算表明，尽管氧杂磷杂环丙烷配合物3中的CO键更容易裂解，但只有PC键裂解中间体6才能使动力学上有利的PN环闭合，从而得到4中的双环P-配体。配合物3c与原位生成的Ti（III）配合物反应，得到磷烯烃配合物10c，杂核复合物10c.ZnCl2和P，N-螯合物11c。

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《Dalton transactions: An international journal of inorganic chemistry》 |2016年第5期|共10页
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Klein Melina; Schnakenburg Gregor; Espinosa Ferao Arturo; Streubel Rainer;
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1. Rearrangement and deoxygenation of 3,3-bis(2-pyridyl) oxaphosphirane complexes [J] . Klein Melina, Schnakenburg Gregor, Espinosa Ferao Arturo, Dalton transactions: An international journal of inorganic chemistry . 2016,第5期

机译：3,3-双（2-吡啶基）氧杂磷杂环丙烷配合物的重排和脱氧
2. A new route to phosphaalkene chelate complexes: SET deoxygenation of oxaphosphirane complexes followed by intramolecular CO substitution [J] . Klein M., Albrecht C., Schnakenburg G., Organometallics . 2013,第17期

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