Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

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• 作者：Baofei Pan ; Deirdra A. Evers-McGregor ; Mark W. Bezpalko ; Bruce M. Foxman ; Christine M. Thomas
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 19, 2013
• 年：2013
• 卷：52
• 期：16
• 页码：9583-9589
• 全文大小：390K
• 年卷期：v.52,no.16(August 19, 2013)
• ISSN：1520-510X

文摘

By incorporating an N-heterocyclic phosphenium/phosphide (NHP) ligand into a chelating pincer ligand framework (PPP⁺/PPP^{鈥?/sup>), we have elucidated several different and unprecedented binding modes of NHP ligands in homobimetallic, heterobimetallic, and trimetallic metal complexes. One-electron reduction of the previously reported (PPP)鈭?/sup>/MII complexes (PPP)M-Cl (M = Pd (1), Pt (2)) results in clean formation of the symmetric homobimetallic MI/MI complexes [(渭-PPP)Pd]₂ (5) and [(渭-PPP)Pt]₂ (6). The tridentate NHP ligand has also been utilized as a bridging linker in the M/Co heterobimetallic compounds (OC)₃Co(u-PPP)M(CO) (M = Pd (7), Pt (8)), synthesized via salt elimination from mixtures of 1 and 2 and Na[Co(CO)₄]. Furthermore, an NHP-bridged trimetallic complex (PPP)₂Pd₃Cl₂ (9) can be synthesized in a manner similar to precursor 1 (Pd(PPh₃)₄ + (PPP)Cl) via careful adjustment of reaction stoichiometry. Examination of the interatomic distances and angles in complexes 5鈥?b>9, in tandem with density functional theory calculations have been used to evaluate and characterize the bonding interactions in these complexes.}