she is grateful___ Mr.Tmith___ all that he had done填介词,

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she is grateful___ Mr.Tmith___ all that he had done填介词,
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she is grateful___ Mr.Tmith___ all that he had done填介词,
she is grateful___ Mr.Tmith___ all that he had done
填介词,

she is grateful___ Mr.Tmith___ all that he had done填介词,
to...for
be grateful to sb for sth
由于某事而感激某人

be grateful to sb for sth 因为(for)某事对(to)某人很感激。
所以答案为to for