Kinetic Study of Ligand Exchange in mu-(2,2,8,8-Tetramethyl-3,7- Dithianonane)-Decacarbonylditungsten(0)

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The substitution reaction of (DTN)W2 (CO)10 with P(OCH(CH3 )2 )3 is a stepwise reaction. The kinetics of step 1 follow the equation: -d[substrate] /dt = kld [substrate] + k la [substrate] [ligand]. Thus the mechanism of step 1 is expected to be a competition between dissociative and associative pathways. The kinetics of step 2 follow the equation: -d[(DTN)W(CO)5]/dt = k2dk3[(DTN)W(CO)5][ligand]/k-2[DTN] + k3[ligand] The plot of kobsd versus [ligand] thus is a hyperbolic curve and the plot of 1/kobsd versus 1/[L] exhibits linear behavior. A mechanism for step 2 in which (DTN)W(CO)5 dissociates to an intermediate, W(CO) 5 , and in ... continued below

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vi, 42 leaves: ill.

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Yang, Sang-Nin May 1982.

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  • Yang, Sang-Nin

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The substitution reaction of (DTN)W2 (CO)10 with P(OCH(CH3 )2 )3 is a stepwise reaction. The kinetics of step 1 follow the equation: -d[substrate] /dt = kld [substrate] + k la [substrate] [ligand]. Thus the mechanism of step 1 is expected to be a competition between dissociative and associative pathways. The kinetics of step 2 follow the equation: -d[(DTN)W(CO)5]/dt = k2dk3[(DTN)W(CO)5][ligand]/k-2[DTN] + k3[ligand] The plot of kobsd versus [ligand] thus is a hyperbolic curve and the plot of 1/kobsd versus 1/[L] exhibits linear behavior. A mechanism for step 2 in which (DTN)W(CO)5 dissociates to an intermediate, W(CO) 5 , and in which DTN and P(OCH(CH3 )2 )3 compete to associate with W(CO) 5 is favored. The dissociative rate constant of the first step, kld' is about 1.2 times of that of the second step, k2d. The dissociation of (DTN)W(CO) 5 from (DTN)W2 (CO) 1 0 is favored over the dissociation of DTN from (DTN)W(CO) 5 due to a combination of the steric, stoichiometric, charge repulsion and entropy effects of the reaction.

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vi, 42 leaves: ill.

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  • May 1982

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  • May 10, 2015, 6:16 a.m.

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  • Jan. 11, 2017, 2:47 p.m.

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Yang, Sang-Nin. Kinetic Study of Ligand Exchange in mu-(2,2,8,8-Tetramethyl-3,7- Dithianonane)-Decacarbonylditungsten(0), thesis, May 1982; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc503931/: accessed July 15, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .