No, the first screenshot shows that Ctrl+6 is assigned to the command currently selected in the Commands field, namely Tool06. You need to do the following:
In Commands, click PHP Program 2.
Click the field under Press new shortcut key.
Press the Ctrl+6 key.
Click Assign.
and repeat the process for PHP DOS Command 2 and Ctrl+7.
Did you try the steps I gave in my previous reply? Did they work?
I don't know why you're seeing Tool06 and Tool07 in the Commands field of your Preferences dialog. Since you have seven external tools defined, I would have expected to see the names of your seven tools followed by Tool08, Tool09, etc.
Nevertheless, I can see from your screenshot that Ctrl+6 is not assigned to PHP Program 2.
The numbers in the icons in the second screenshot of the 07.Nov.2016 04:51 posting, within the green frame, show 10 and 11 - thus I assume that "PHP Program 2" is Tool 10 and "PHP DOS Command 2" is Tool 11.
Mind timezone settings. For me the post was created at 02:51 +0000, so you seem to use +0200, and we both don't know which timezone the author was using.
To directly link to a post use this icon, which you find in front of the posting date/time.