Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex
Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex
复制标题
N-杂环磷脂复合物 Co-P 键上 O-H 和 S-H 键的协同激活
DOI：
10.1039/c8dt05052j
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发表时间：
2019
影响因子：
4
通讯作者：
Thomas, Christine M.
中科院分区：
文献类型：
--
作者：
Poitras, Andrew M.;Bezpalko, Mark W.;Foxman, Bruce M.;Thomas, Christine M.
金属-配体合作已被证明是σ键活化和催化的可行概念，然而很少有涉及磷作为键断裂的积极参与者的例子。研究了三齿N-杂环膦（NHP-）配体与二膦侧臂（PPP）-连接的钴（I）中心的金属-磷键之间的E-H键（E = S，O）的反应性。将PhOH加成到（PPP）CoPMe 3（1）中干净地得到（PPOPhP）Co（H）PMe 3（2），其中O-H键在M-PNHP键上异裂。PhSH与1加成首先生成（PPHP）Co（SPh）PMe 3（3），其经历分子间重排生成（PPSPhP）Co（H）PMe 3（4）作为热力学产物。与相关铂（II）系统的比较揭示了金属固有性质的变化对金属-配体双官能σ键活化过程的微妙影响。
Metal–ligand cooperation has proven to be a viable concept for σ bond activation and catalysis, however there are few examples involving phosphorus as an active participant in bond cleavage. The reactivity of E–H bonds (E = S, O) across a metal–phosphorus bond of a cobalt(I) center ligated by a tridenate N-heterocyclic phosphido (NHP−) ligand with diphosphine sidearms, (PPP)−, has been explored. Addition of PhOH to (PPP)CoPMe3 (1) cleanly affords (PPOPhP)Co(H)PMe3 (2), in which the O–H bond was heterolytically cleaved across the M–PNHP bond. Addition of PhSH to 1 first generates (PPHP)Co(SPh)PMe3 (3), which undergoes an intermolecular rearrangement to generate (PPSPhP)Co(H)PMe3 (4) as the thermodynamic product. A comparison with a related platinum(II) system reveals the subtle effects that variations in metal intrinsic properties can have on metal–ligand bifunctional σ bond activation processes.