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Our prior work (14) is certainly not the first example of a well-characterized organometallic precatalyst. Extensive examples of well-characterized organometallic precatalysts can be found in
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Our prior work (14) is certainly not the first example of a well-characterized organometallic precatalyst. Extensive examples of well-characterized organometallic precatalysts can be found in: Zakharov, V. A.; Yermakov, Y. I. Catal. Rev.-Sci. Eng. 1979, 19, 67
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Eds.; Wiley-VCH: Weinheim,. However, ours is the first study that starts from a well-characterized speciation-controlled supported organometallic precatalyst and focuses on supported-nanoparticle heterogeneous catalyst formation in contact with solution, and which contains the necessary kinetic data to rule out alternative mechanisms en route to a kinetically supported proposed mechanism.
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Modern Surface Organometallic Chemistry; Basset, J.-M.; Psaro, R.; Roberto, D.; Ugo, R., Eds.; Wiley-VCH: Weinheim, 2009. However, ours is the first study that starts from a well-characterized speciation-controlled supported organometallic precatalyst and focuses on supported-nanoparticle heterogeneous catalyst formation in contact with solution, and which contains the necessary kinetic data to rule out alternative mechanisms en route to a kinetically supported proposed mechanism.
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3 supported-nanoparticle heterogeneous catalyst (confirmed for the present system by transmission electron microscopy (TEM) and XAFS (14)). In addition, a prototype system should: (iv) yield an active and long-lived catalyst, and hence (v) provide a system where the initial kinetic and mechanistic studies of the in situ catalyst formation are worth the effort. The prototype system should also yield (vi) reproducible and quantitative kinetic data so that quantitative conclusions and mechanistic insights can be drawn; and ideally (vii) comparison to a kinetically and mechanistically well-studied nanoparticle formation system in solution should also be possible for any insights that comparison might allow. (4, 34, 45) Last, once that prototype system is in hand, one would also like to (viii) systematically vary key synthetic variables such as the support, solvent, and metal precursor to reveal their affects on supported-nanoparticle formation in contact with solution.
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3 wt % as was done in the present studies
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3 wt % as was done in the present studies.
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101
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79957750122
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3 precatalyst preparation and subsequent supported-nanoparticle heterogeneous catalyst formation kinetics. (14) Hence, it follows that only samples prepared under the same synthetic conditions should be (and were) plotted in Figures 2 and 3
-
3 precatalyst preparation and subsequent supported-nanoparticle heterogeneous catalyst formation kinetics. (14) Hence, it follows that only samples prepared under the same synthetic conditions should be (and were) plotted in Figures 2 and 3.
-
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102
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79957693330
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In neat cyclohexane, the UV-vis spectrum of the filtered solution (Figure S3 in the Supporting Information) reveals that no Ir(1,5-COD)Cl(solvent) is present in solution. However, in acetone, two metal-to-ligand charge transfer bands are present from 340 to 540 nm (detailed in the Supporting Information), data consistent with the presence of a square planar Ir(I) complex in acetone. (39)
-
In neat cyclohexane, the UV-vis spectrum of the filtered solution (Figure S3 in the Supporting Information) reveals that no Ir(1,5-COD)Cl(solvent) is present in solution. However, in acetone, two metal-to-ligand charge transfer bands are present from 340 to 540 nm (detailed in the Supporting Information), data consistent with the presence of a square planar Ir(I) complex in acetone. (39)
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2 and, therefore, is not MTL under these conditions). (4)
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2 and, therefore, is not MTL under these conditions). (4)
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sus and [acetone] data
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sus and [acetone] data.
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