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4 (and, indeed, are experimentally apparent in the present work, such as the lack of a critical coagulation concentration for the polyxoanion-stabilized Ir(0) nanoclusters used in the present work). However, for the sake of simplicity, herein, we have chosen to distinguish the terms "nanocluster" from "colloid" or "nanocolloid" only where we felt it was important.
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∼900 nanoclusters.
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The reader may wonder if the change in solvent from that employed in many of our earlier studies, acetone, to propylene carbonate, can contribute to a change in mechanism. The data in Table S1 of the Supporting Information demonstrate that the answer is no, at least in the present case and under the specific conditions used in the present studies.
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The reader may wonder if the change in solvent from that employed in many of our earlier studies, acetone, to propylene carbonate, can contribute to a change in mechanism. The data in Table S1 of the Supporting Information demonstrate that the answer is no, at least in the present case and under the specific conditions used in the present studies.
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3‡; = 6.2(3) kcal/mol is, therefore, larger than just the barrier to diffusion in propylene carbonate, so that other factors besides diffusion must be introducing a barrier into the B + B - C agglomeration process.
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3‡; = 6.2(3) kcal/mol is, therefore, larger than just the barrier to diffusion in propylene carbonate, so that other factors besides diffusion must be introducing a barrier into the B + B - C agglomeration process.
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Intriguing mechanistic questions are opened up by these findings. One is whether an associative mechanism occurs via bridging ligands that might, conceivably, bind the two metal particles, thereby giving the surface ligands more time to move, leaving larger bare-metal spots that are presumably key to the metal-metal bond formation process that leads to larger metal aggregates. Alternatively, another interesting question is if there are sufficient bare-metal spots on the surface of the nanocluster to support a direct, associative agglomeration, or is a mere single, bare-metal atom sufficient to initiate agglomeration? A third important question is how much the olefin (i.e, the cyclohexene used in the reporter reaction) is influencing the observed activation parameters, something that should be addressable by examining other olefins or, better, repeats of the present studies by other methods without and then with cyclohexene, H2, and then both cyclohexene and H 2pr
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2present.
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