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首页> 外文期刊>Chemistry: A European journal >Exocyclic bond cleavage in oxaphosphirane complexes?
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Exocyclic bond cleavage in oxaphosphirane complexes?

机译：氧杂磷杂环戊烷配合物中的环外键裂解？

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摘要

A first computational insight into the intrinsic strength of exocyclic bonds to phosphorus in oxaphosphirane κP-pentacarbonylmetal(0) complexes 1 a-f (M=Cr, Mo) is provided using a set of P-R derivatives (R=Me, tBu, CPh _3). Whereas homolytic cleavage of the exocyclic P-R bond was found to be always unfavored (for neutral complexes), heterolytic cleavage leading to a carbocation R ~+ moiety and the oxaphosphiranide complex 2 ~- constitutes the lowest-energy process, especially if R is bulky and can stabilize the positive charge, that is, triphenylmethyl (trityl), efficiently. The energies required for P-M bond cleavage are about 30 kcal mol ~(-1), and decrease with the increasing bulk of the R substituent (from Me to trityl) and ongoing from Cr to Mo. The reactivities of complexes 1 a-f towards oxidative and reductive single electron transfer (SET) reactions were analyzed using the facile variation of bond-strength-related descriptors (VBSD) methodology, thus enabling the design of synthetically useful strategies addressing decomplexation and P-functionalization. Reductive SET reactions with sodium naphthalenides enable selective P-M bond cleavage (i.e., decomplexation) for the case of P-Me and P-tBu substitution, whereas reductive P-R bond cleavage is favored in the case of the P-trityl complexes 1 c,f, and results in the formation of the (anionic) oxaphosphiranide complex 2 -, which may be regarded as a potential key intermediate for further P-functionalization.
机译：使用一组P-R衍生物（R = Me，tBu，CPh _3）提供了对氧杂磷杂环戊烷κP-五羰基金属（0）配合物1 a-f（M = Cr，Mo）中磷的环键固有强度的第一计算见解。尽管发现环外PR键的均裂总是不利的（对于中性配合物），导致碳正离子R〜+部分和草酰氧磷杂合物2〜-的杂合裂解构成了最低的能量过程，特别是如果R体积大且可以有效地稳定正电荷，即三苯甲基（三苯甲基）。 PM键断裂所需的能量约为30 kcal mol〜（-1），并随着R取代基的增加（从Me到三苯甲基）和从Cr到Mo的增加而降低。配合物1af对氧化和还原的反应性还原性单电子转移（SET）反应使用键强度相关描述符（VBSD）方法的简便变化进行了分析，从而能够设计用于解决复合和P功能化的合成策略。在P-Me和P-tBu取代的情况下，与萘钠的还原性SET反应可实现选择性的PM键裂解（即，解聚），而在P-三苯甲基配合物1 c，f，并导致形成（阴离子）氧杂磷酰胺化物配合物2-，可以将其视为进一步P-官能化的潜在关键中间体。

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