She accused him of having broken his word.
vorwerfen = to accuse
I’ve more often heard “beschuldigen” for this meaning, but it seems that vorwerfen and beschuldigen are synonyms (at least according to google… I’ve never seen the word vorwerfen before now).
“vorwerfen” goes (or can go) more in the direction of “to reproach”, i.e. there are emotions attached, while “beschuldigen” is more neutral.
In English when one “throws something up to somebody” it means to accuse them. “She threw it up to him that he was a liar.” I don’t think it’s very common now, as “to throw up” is pretty well stuck to vomiting. Unfortunately.