Title of article :
Synthesis of [Ru3(CO)9(μ-dppf){P(C4H3E)3}] (E = O, S) and thermally induced cyclometalation to form [(μ-H)Ru3(CO)7(μ-dppf){μ3-(C4H3E)2P(C4H2E)}] (dppf = 1,1′-bis(diphenylphosphino)ferrocene)
Author/Authors :
Md. Kamal Hossain، نويسنده , , Subas Rajbangshi، نويسنده , , Ahibur Rahaman، نويسنده , , Md. Arshad H. Chowdhury، نويسنده , , Tasneem A. Siddiquee، نويسنده , , Shishir Ghosh، نويسنده , , Michael G. Richmond*، نويسنده , , Ebbe Nordlander، نويسنده , , Graeme Hogarth، نويسنده , , Shariff E. Kabir، نويسنده ,
Issue Information :
دوفصلنامه با شماره پیاپی سال 2014
Pages :
9
From page :
231
To page :
239
Abstract :
The new clusters [Ru3(CO)9(μ-dppf){P(C4H3E)3}] (1, E = O; 2, E = S) have been prepared from the Me3NO-induced decarbonylation of [Ru3(CO)10(μ-dppf)] in the presence of PFu3 (E = O) and PTh3 (E = S), respectively. Upon thermolysis in benzene, the major products are the cyclometalated clusters [(μ-H)Ru3(CO)7(μ-dppf){μ3-(C4H3E)2P(C4H2E)}] (3, E = O; 4, E = S). This thermolytic behavior is in marked contrast to that previously noted for the analogous bis(diphenylphosphino)methane (dppm) complexes [Ru3(CO)9(μ-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(μ-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 “windshield wiper” motion of the activated thienyl moiety determined.
Keywords :
Trifurylphosphine , Trithienylphosphine , Triruthenium , Cyclometalation , Diphosphine , DFT
Journal title :
Journal of Organometallic Chemistry
Serial Year :
2014
Journal title :
Journal of Organometallic Chemistry
Record number :
1370462
Link To Document :
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