Are you trying to set a back-end language or do you want to change the language of your primary/root site in your MS installation?
The back-end language can be set per-user in the user profile.
For changing the language of the first blog you can tell MLP what language to use in Network Admin -> Sites
This, however, will not change the actual post content and everything else in the site. So instead, you would need to tell WP what site ID to use as the default site. Unfortunately, this is a lot more involving, so make sure you are confident with that and have made neccessary backups.
I am assuming you want to change which site shows up under yoursite.com/ (as opposed to yoursite.com/en or yoursite.com/es). Is that right?
Is your Multisite a subdirectory installation? If so, you can try to do the following
Editing this in your wp-config.php is the first part:
define('SITE_ID_CURRENT_SITE', 1);
define('BLOG_ID_CURRENT_SITE', 1);
Change 1 to the blog ID of the site you want to use as the default. You then need to change your *_blogs table in your database. (So wp_blogs for example)
You will see a columns called “paths” This is where you can change the URL of your blogs. Edit the paths according to your desired new setup and give it a try.
Disclaimer: This is general Multisite maintenance and has nothing to do with MLP specifically. What I suggested is untested and may break your site. Be very careful with this and always be prepared to roll back your back-up when something goes wrong