Synthesis of [Ru₃(CO)₉(渭-dppf){P(C₄H₃E)₃}] (E聽=聽O, S) and thermally induced cyclometalation to form [(渭-H)Ru₃(CO)₇(渭-dppf){渭₃-(C₄H₃E)₂P(C₄H₂E)}] (dppf聽=聽1,1鈥?bis(diphenylphosphino)ferrocene)

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• 作者：Md. Kamal Hossain^a ; ^b ; Subas Rajbangshi^b ; Ahibur Rahaman^a ; ^b ; Md. Arshad H. Chowdhury^b ; Tasneem A. Siddiquee^c ; Shishir Ghosh^b ; ^d ; Michael G. Richmond^e ; Ebbe Nordlander^a ; Graeme Hogarth^d ; ^{g.hogarth@ucl.ac.uk" class="auth_mail} ; Shariff E. Kabir^b ;
• 关键词：Triruthenium ; Trifurylphosphine ; Trithienylphosphine ; Cyclometalation ; Diphosphine ; DFT
• 刊名：Journal of Organometallic Chemistry
• 出版年：15 June, 2014
• 年：2014
• 卷：760
• 期：Complete
• 页码：231-239
• 全文大小：897 K

文摘

The new clusters [Ru₃(CO)₉(渭-dppf){P(C₄H₃E)₃}] (1, E聽=聽O; 2, E聽=聽S) have been prepared from the Me₃NO-induced decarbonylation of [Ru₃(CO)₁₀(渭-dppf)] in the presence of PFu₃ (E聽=聽O) and PTh₃ (E聽=聽S), respectively. Upon thermolysis in benzene, the major products are the cyclometalated clusters [(渭-H)Ru₃(CO)₇(渭-dppf){渭₃-(C₄H₃E)₂P(C₄H₂E)}] (3, E聽=聽O; 4, E聽=聽S). This thermolytic behavior is in marked contrast to that previously noted for the analogous bis(diphenylphosphino)methane (dppm) complexes [Ru₃(CO)₉(渭-dppm){P(C₄H₃E)₃}], in which both carbon-hydrogen and carbon-phosphorus bond activation yields furyne- and thiophyne-capped clusters. The crystal structures of 1, 3 and 4 are presented and reveal that phosphine migration has occurred during the transformation of 1,2 into 3,4, respectively. The possible relation of the observed reactivity to the relative flexibilities of the diphosphine ligands is discussed. Density functional calculations have been performed on the model cluster [Ru₃(CO)₉(渭-Me₄-dppf){P(C₄H₃O)₃]}], and these data are discussed relative to the ground-state energy differences extant between the different isomeric forms of this cluster. The dynamic NMR behavior displayed by the metalated thienyl ring in cluster 4 has also been investigated by computational methods, and the free energy of activation for the 鈥渨indshield wiper鈥?motion of the activated thienyl moiety determined.