Puedes usar un UPDATE
con un JOIN
a una tabla derivada para esto:
UPDATE Items AS i1
JOIN (
SELECT ID, @n := @n + 1 AS Image
FROM Items
CROSS JOIN (SELECT @n := (SELECT MAX(Image) FROM Items)) AS v
WHERE Image IS NULL
ORDER BY ID
) AS i2 ON i1.ID = i2.ID
SET i1.Image = i2.Image;
La tabla derivada usa variables para calcular la Image
valores de los registros que tienen NULL
s.