Used to be called Kuler, and it was an extension you could pick up through the Adobe Extension service. Quite handy, you can also DL the App on iOS, or just bookmark to main screen from Chrome on Android. Now it's called Adobe Color CC. Super handy if you find yourself looking to reference particular color schemes. Complimentary color, as presented in the video is only one scheme, there are a too many to go into in a post, or even a 15 minute video.
http://www.amazon.com/Color-Design-Workbook-World-Graphic/dp/1592534333/ref=sr_1_11?ie=UTF8&qid=1415889694&sr=8-11&keywords=color+theory here's a great book for anyone wishing to investigate further on why you would want to use different rules. And how/when to apply them for desired effect.
one thing Aaron didn't point out, when you make a swatch, you could just import the swatch from the web, or iOS app into the swatches panel so you don't have to screen cap. Although Screen capping would work great for non PS users, as last I knew the browser version is free.
https://color.adobe.com/create/color-wheel/
