When you port from provider A to provider B, routing data is placed on the core/central network of both providers as mobile networks route calls based on network-allocated prefixes.
Provider A will receive calls from other operators and need to forward them to provider B. Provider B wants to avoid sending calls from within their own network, to provider A but instead keep them on-network.
In your case, it's likely provider A's data that needs correcting but as you are now with provider-B, it's upto them to resolve it. Checking that the theory of "all calls from provider A are affected" is often an excellent start in these scenarios, and will establish whether this is the correct course.
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I've looked into this on my part and all of the details to do with the SIM etc are fine, nothing at all suggests to me a reason as to why your wife shouldn't be able to call you successfully. It looks to be an issue with the 02 phone itself so I'd suggest having a look into this, let me know how it goes.
Travis, Thanks for your reply. Just awaiting a new sim card from o2 as they don't have a clue why this is occurring at all. So once it has arrived and has replaced the old sim will keep you updated as too if this has fixed the problem or not.
@Katie_WT Messing with settings on people’s phones can be a real pain for them. In this case, why not just have the customer turn off their phone removing it from the network? That way if his wife still can’t call him it eliminates device setting issues and proves the network can’t route the call.
I had the same issue which took three weeks to resolve, it was an error in the porting.