Here's your continuum:
Atom --> Cluster --> Nanoparticle --> Bulk material
The properties of each of these can be quite different, mostly because chemistry happens at the surface of a material. In the case of an atom, these are typically so reactive that they are rarely "floating about" in the charge zero state - even in gas phase, with the exception of noble gasses. So a "metal center" will usually be a metal atom, in a formal nonzero oxidation state, bound by some stabilizing ligand or organic/inorganic framework. An example might be a metal porphyrin. The type of chemistry that can be occur at, say, the iron bound to a porphyrin, may be quite different from that able to occur at an iron nanoparticle... or a macroscale lump of iron. Some of this difference may be simply kinetic, but not all of it.