You can add a bar button of type UIBarButtonSystemItemFlexibaleSpace in the place where you want the space.
UIBarButtonItem *barButton1 = ...
UIBarButtonItem *barButton2 = ...
UIBarButtonItem *flexibleSpaceBarButton = [[UIBarButtonItem alloc]
initWithBarButtonSystemItem:UIBarButtonSystemItemFlexibleSpace
target:nil
action:nil];
toolbar.items = [NSArray arrayWithObjects:barButton1,
flexibleSpaceBarButton,
barButton2, nil];