Not sure what that promo photo is for or if it means anything. Are you saying the DeVille was worn by Sean Connery in From Russia with Love? Or was it another character that wore it? I've never seen Sean Connery wear an Omega in any Bond film. Do you have any photos of him wearing it in From Russia with Love? Here is a site showing the Submariner Connery wore in From Russia with Love. http://watchesinmovies.info/movies/from-russia-with-love-1963/
They have a full list of watches worn in the Bond films with photos, and it mentions Rolex, Hamilton, Seiko, Breitling, and Omega, but Omega is not listed for anything prior to Goldeneye with Pierce Brosnan. I also looked on Omega's website and there is a section on James Bond, but they don't talk about Bond wearing an Omega before Goldeneye. Another site says before Omega was worn by Bond he wore Rolex watches (and they list From Russia with Love as one where he wore a Rolex. http://www.jamesbondlifestyle.com/product/rolex I'm just curious what scene or which character wore the Omega DeVille in the photo you submitted. If he wore it and you never see it in the film, it makes it sort of irrelevant.
Bond DID drive a Z3, in Goldeneye. He drove a Z8 in a later movie, The World is Not Enough.