The pitch for Thrawn: Alliances is a good one and Zahn knows it: put Thrawn in a room with Darth Vader, and give the reader the private knowledge that the two of them have met before, when one of them was Anakin Skywalker. Everything in the novel runs off that single asymmetry.
The structure
Two timelines, alternating. In the Clone Wars strand, Jedi General Anakin Skywalker and a Chiss officer called Mitth’raw’nuruodo cooperate on a mission in the Unknown Regions, with Padmé Amidala’s own investigation running alongside. In the Imperial strand, the Emperor sends Thrawn and Vader back to the same region to look into a disturbance, and neither of them is willing to be the first to say what he remembers.
The chapters are cut so that a beat in one timeline lands on the answering beat in the other. When it works — and for two thirds of the book it works very well — it produces the rare tie-in novel where the form is doing the argument.
Vader
This is the strongest Vader prose has managed in canon. He is not a rage engine here; he is a man conducting an interrogation of someone he cannot afford to let finish a sentence. Every scene between the two is Thrawn probing and Vader refusing, and because we know exactly what is being refused, the tension does not need a plot to carry it.
Padmé
The genuine surprise. Zahn gives her an infiltration plot of her own, competently run, with no romance ballast attached, and she is better company than either of the men. It is a small correction to a large problem — see the dossier — but it is a real one.
Where it loses grip
The plot the two timelines are hung on is thin. The Grysk threat is introduced as an ominous shape and stays a shape; the mission objectives in both eras are functional rather than interesting; and the final act resolves through a technical solution that the book has not made the reader care about. Take away the structural trick and there is not much novel underneath.
Where it sits
Second of three in the canon trilogy, after Thrawn and before Treason. It is also the book that connects the canon Thrawn to Batuu and, eventually, to the wider Unknown Regions material. Read it in order; it assumes you know who Eli Vanto was.
Who should read it
People who liked the first book and want the Vader scenes everyone told them about. They are worth it. Just do not expect the surrounding novel to match them.