From Neutral to Anionic η1-Carbon Ligands: Experimental Synthesis and Theoretical Analysis of a Rhodium−Yldiide Complex

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• 作者：Remigiusz Zurawinski^† ; ; Christine Lepetit^‡ ; ^§ ; ; Yves Canac^‡ ; ^§ ; ; Marian Mikolajczyk^† ; ; Remi Chauvin*^R
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：March 2, 2009
• 年：2009
• 卷：48
• 期：5
• 页码：2147-2155
• 全文大小：332K
• 年卷期：v.48,no.5(March 2, 2009)
• ISSN：1520-510X

文摘

Deprotonation of a cationic rhodium complex of a chelating semistabilized phosphino−phosphonium sulfinyl−ylide ligand afforded the neutral complex of the corresponding yldiide ligand. Despite the limited stability of the yldiide complex its structure was ascertained by ESI MS and multinuclear ¹H, ³¹P, ¹³C, and ¹⁰³Rh NMR spectroscopy. DFT calculations were carried out at the B3PW91/6-31G*/LANL2DZ*(Rh) level to derive a reasonable gas-phase structure for the yldiide complex or model thereof and gain insight into their electronic structure. ELF and AIM topological analyses were used to investigate the metal−ligand bonding and estimate the electron transfer resulting from proton abstraction. ELF weighting of the resonance forms of the anionic “free” yldiide ligand (Ar₃PC⁻−S(O)Ar) was compared to the corresponding weighting of previously reported neutral counterparts (XCY), namely, bis-α-zwitterionic bisylides of phosphonium, sulfonium, or iminosulfonium moieties (X, Y = PR₃, SR₂, S(NMe)R₂). The results suggest that the phosphonium sulfinylyldiide can be regarded as a tris-α,β-zwitteranionic bisylide (Ar₃P⁺−C²⁻−S⁺(−O⁻)p-Tol).