(New) Buttons not showing on toolbar

I created a new toolbar and added a couple of buttons (in version 10.0.0.3). I have now added a couple more (in 10.0.0.6). They show in customise mode:

(the last two buttons on the right)

But do not show when not in customise mode:

Is there an issue or have I done something wrong?

What commands do those buttons run?

Thank you. The command syntax I choose was wrong (did not work). Once corrected the button appeared.