Synthesis, Structure, and Temperature-Dependent Dynamics of Neutral Palladium Allyl Complexes of Annulated Diaminocarbenes and Their Catalytic Application for C−C and C−N Bond Formation Re

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• 作者：Sarim Dastgir ; Karl S. Coleman ; Andrew R. Cowley ; Malcolm L. H. Green
• 刊名：Organometallics
• 出版年：2010
• 出版时间：November 8, 2010
• 年：2010
• 卷：29
• 期：21
• 页码：4858-4870
• 全文大小：1237K
• 年卷期：v.29,no.21(November 8, 2010)
• ISSN：1520-6041

文摘

Imidazolinium salts 7,9-bis(2,4,6-trimethylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolinium tetrafluoroborate and 7,9-bis(2,6-diisopropylphenyl)-6b,9a-dihydroacenaphtho[1,2-d]imidazolinium tetrafluoroborate, designated as [(BIAN-SIMes)(H)]BF<sub>4sub> (3a) and [(BIAN-SIPr)(H)]BF<sub>4sub> (3b), respectively, have been prepared and structurally characterized. The molecular structure of 3a shows the presence of a bifurcated hydrogen bond between the tetrafluoroborate anions and the central imidazolinium proton (−NCHN−). The palladium(II) complexes (η<sup>3sup>-C<sub>3sub>H<sub>5sub>)Pd(BIAN-SIMes)Cl (5a) and (η<sup>3sup>-C<sub>3sub>H<sub>5sub>)Pd(BIAN-SIPr)Cl (5b) have been synthesized. The temperature-dependent NMR behavior of σ-bonded palladium(II) complex 5b was studied. The crystal structure of 5b shows a localized single and double bond between the allyl ligand. The catalytic activities of the palladium(II) complexes 5a and 5b have been evaluated for Suzuki-type C−C coupling and for room-temperature C−N bond formation using aryl halides.