They are and they have; see US v. Adobe Systems Inc., et al. From the wiki article:
"DOJ alleged in their Complaint that the companies had reached "facially anticompetitive" agreements that "eliminated a significant form of competition...to the detriment of the affected employees who were likely deprived of competitively important information and access to better job opportunities."
https://en.wikipedia.org/wiki/High-Tech_Employee_Antitrust_L...
Unions organize in public, employers collude in secret. The fact that the companies proposed a settlement the day the suit was filed indicates they simply priced that into their cost-benefit analysis when they were colluding.
So what would this employers' union do exactly?
There are sufficient number of software and database companies to establish an employer organisation for software.