Nothing is strongly referencing your view controller (ThingViewController), other than the local variable in -applicationDidFinishLaunching:. Once that goes out of scope, the view controller is released and dealloc'ed. The view itself is still around, since it is a subview of your window's contentView.
Once your view controller is released/gone, the text field has no connection back to the Thing object so it is in effect calling [nil setValue:@"New first name" forKeyPath:@"representedObject.firstName"].
Add a strong reference to your view controller (e.g., an instance variable of your app delegate) and try it again.
@implementation AppDelegate {
Thing *theThing;
ThingViewController *vc;
}
- (void)applicationDidFinishLaunching:(NSNotification *)aNotification
{
NSView *cv = self.window.contentView;
vc = [[ThingViewController alloc] initWithNibName:@"ThingViewController" bundle:nil];
theThing = [Thing new];
theThing.firstName = @"Rob";
vc.representedObject = theThing;
[cv addSubview:vc.view];
}