Yes, you need to create new NSException object, copy/add parts you want to have there and call raise again.
@catch (NSException* exception)
{
NSMutableDictionary* d = [[exception userInfo] mutableCopy];
[d setObject:@"new info" forKey:@"newKey"];
NSException * e = [NSException exceptionWithName:[exception name] reason:[exception reason] userInfo:d];
[e raise];
}