Typically in defamation law, claims made persuiant to litigation are not defamatory, since they are going to be tested for validity if the case goes to trial. I'm not familiar with any differences in what is generally done in settlements between the U.K. and the U.S., but since both are Common Law countries, and Settlements are very common in civil proceedings in the U.S., it's a good start.
Generally a settlemant can occur anytime before the verdict of the case is rendered, although usually it will happen after preliminary hearings during the Discovery phase. In the U.S., Discovery is very broad and one need not prove that the requested items contain evidence but might contain evidence. This means that, for example, you could request a substantial amount of e-mail records from the opposing party because somewhere on the company e-mail server, there might be something to help your case. And even if after you sift through the emails and find no smoking guns related to your case, you could find some dirty laundry that's unrelated but still damning... if not more so than the initial case. Many people, especially big compainies, would rather just give the ex-employee some what he/she wants, if it means they don't get to see the proverbial man behind the curtain.
Additionally the practice might fall into a legally gray area of the law that, if it reaches trial, could hurt the company or even the industry if a judge rules against the company, effectively saying that this gray area is now definately illegal. Better to eat the loss of capital with the settling out of court than to take the much larger hit of the buisness practice being illegalized all together.
Typically in settlements, both parties agree to terms and sign a contract. While the whole of the terms are never discussed, almost all include that the plaintiff will drop the case and never bring the matter to court again and that both parties will sign a non-disclosure agreement (NDA) meaning that they won't discuss the rest of the settlement terms with anyone not party to them.
If the plaintiff does break the NDA, the defendant can sue for breech of contract and recover at the least the monitary compensation they awarded in the settlement. Conversely, if the respondent breaks the NDA, the plaintiff can refile their initial suit with the addition of breech of contract (and this time it will get to court... and all the dirty laundry sees the harsh light of day.).
While the respondent in a settled case can possibly sue for defamation if the plaintiff said the respondent did what the initial suit claimed they did (legally, it was never proven or disproven), or they were guilty (again, since no verdict was reached at trial, no guilt was established), the breech of contract is a much more airtight case and doesn't open up discovery to the respondent's cupability in the settled case (since the breech is about discussing the settled case at all, not the validity of the accusations of the settled case). Typically they would not go this route because then it opens the can of worms the settlement was trying to keep a lid on.