Although the Model Materials are the ones you see in the Materials-Browser, SketchUp has two other types of Materials - those associated with Layers and those associated with Images.
These cannot be directly accessed using native tools or the API - although there are tricks, like my SKM_tools which has a new_material = image.use_as_material method, which can be used to extract an Image's Material and add it to the Model without Exploding the Image.
If you Explode an Image its Material has a database flag reset so it then appears in then the Model's Materials list [renamed].
It seems that in the case of this Image when it was made into a Material that flag was not reset properly.
Even saving the texture-image as a PNG and reusing that, it still is missing in the Materials-Browser !
On a PC the only way I found of jerking it back into reality was to edit the group-container, select the face that uses the wayward Material [named "Image1"] and use the right-click > context-menu > "Make Unique Texture" - so now the Material "Image1" is duplicated as "Image1#1" - however, you can then rename it "Image1" with no errors, so the origin has vanished... and now all is well !