@frob ,
In order to change the hub navigation bar color, we can go to site settings of hub site>Change the look>under the header section>Background> select a theme color to change the background color of your site header.
Note that the background of the site header(include the hub navigation bar)will depend on your site theme:
----------------------------------------------------Update Answer--------------------------------------------------
Sorry I missed your attached request, if you don't want to depend on the theme, we can add the modern script web part, insert css code to change the backgroud-color of the hub navigation bar:
<style>
.root-42
{
background-color: #B2E23B !important;
}
</style>
Then republish the page to check the result:
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