Alice and Ioan came from similar backgrounds, both middle/lower middle class, both sets of parents were teachers, both of them were actors and both aspirational. Ioan came from a much more sheltered Welsh chapel background than Alice and he was intimidated by the posh students and teachers at RADA, to the point where he wanted to leave after his first year and that is when he got involved with the culty church and his mum rescued him. Alice pretends to be posh with her socialite friends but I was struck by the interviewer in the 2001 Telegraph article remarking that while Alice spoke flawless French without an accent that she spoke English with a Bristol accent.
When Ioan met Alice she was a huge star in France, glamorous, used to socializing and being the center of attention, and being shyer she was his buffer into that world while at the same time able to be one of the lads with the drinking and crude language. She rescued him as his mother had before and he rescued her when she was in mourning and in what sounded like a stale relationship. I think they saw themselves as a team who were going to conquer Hollywood and they were in love.
For whatever reason Ioan wasn't in a hurry to get married, marriage is less of a big deal in the UK than it is in the US but also while neither of his siblings is married that is not to say they are not in or haven't had long term relationships, maybe marriage isn't important to them and perhaps it wasn't to Ioan. When Alice gave Ioan an ultimatum, her biological clock was ticking, they had been living in the US for a few years and she would have been asked constantly whether marriage was on the cards, and more significantly Ioan had done one Fantastic Four film and was signed up for the F4 franchise so she wanted it official. His attorney and financial advisors would have insisted on the pre-nup and Alice agreed because she thought she was going to be a big star and she wanted to get married. Even before they married she was demeaning and diminishing him, he was boring, he should change his name, she started to interfere with his fans. She needed him to be totally dependent on her, she saw herself as the star socially.
Things started to go wrong when he went through various career disappointments and then when he was unemployed for 2 years. He lost his confidence and was depressed and Alice would have been telling him what he had done wrong and what he should have done instead. She would have resented the success of Matthew Rhys and the lifestyle she gave up with OP. Ioan probably started fearing and resenting her. Anytime they went out or were interviewed she would jump in because she thought she was the more interesting one. Her whole identity became wrapped up in being Mrs. Ioan Gruffudd on social media and presenting their perfect 'family', Ioan was her currency, and she constantly invaded his privacy. When he did Harrow, Ioan was away for months he was around normal people and people who treated him with respect and like a star, then he would come home to a resentful, demanding Alice whose drinking had accelerated while he was away.
TLDR. If you treat people like shit for years, don't be surprised when they finally leave