I also have Roberts' new biography and I would suggest that you also take a look at Vincent Cronin's Napoleon Bonaparte: An Intimate Biography. I have found it to be the best of the biographies, but some don't like it as it is sympathetic to Napoleon. It concentrates on Napoleon the man, and on his reforms and how he ruled France and the Empire.
Thompson's and Englund's biographies are also both useful and helpful.
For an operational history I would highly recommend Vincent Esposito's and John Elting's A Military History and Atlas of the Napoleonic Wars. I believe it is superior to Chandler's Campaigns and it was written by soldiers for the study of cadets at the US Military Academy at West Point. The latest edition is by Greenhill in 1999 and the Recommended Reading List at the end of the book is immensely helpful, especially for building a library.
I agree with Tom's listing which is excellent.
When and if you get around to it, there is a plethora of memoirs that should be read, such as those by Parquin, Barres, Caulaincourt, Lavalette, Bourgogne, Fain, Marchand, and others. Cronin's biography has an excellent appendix which covers some of the memoirs of the period as to accuracy and reliablility.