Definitely connect with your boss on LinkedIn. The more often that you, he, and others from your company connect with each other, the more often your company's name and people will show up in search results when someone is looking for a new vendor/supplier. The company can also set up a company page on there.
Try not to associate with chiefs in your association in light of the fact that LinkedIn suggests them under Individuals You Might Know. Associating with chiefs in your association could make a two sided deal issue:
Take into account that the job of a CEO is extremely difficult and demanding. It necessitates making networking contacts not only on well-known social networking sites like LinkedIn, but also in the real world with real people.