Ignoring the fact that Motorola once again tries to claim trademark rights in the term "Talkabout" for its line of FRS HTs:
There are two separate generally accepted concepts of functions that are useful when your radio is on a "repeater" channel; that is, set to transmit on a different frequency than the one that it receives on:
Talkaround and Reverse
Talkaround, which is primarily found on GMRS radios, allows the operator to be on a Repeater Channel, but by the push of a button, immediately convert it to the Simplex Channel on the same frequency.
Reverse, which is primarily found on HAM Radios, allows the operator to be on a Repeater Channel, but by the push of a button, listen to the Repeater Input frequency and transmit on the Repeater Output frequency
So using @WRWK524's example:
Operator 1 has his radio set to Repeater Channel 23 and transmits on 467.550 through a local repeater and listens to replies on the repeater output of 462.550.
Operator 2 has his radio set to Repeater Channel 23 and using Talkaround, he transmits on 462.550 and listens on 462.550 as well.
Now going to the OP's original question:
Yes, Operator 2 can communicate with Operator 1 because when Operator 1 transmits, Operator 2 will hear him on the output of the Repeater; while when Operator 2 transmits, Operator 1 will hear him Simplex because they are in close proximity.
This will cause some confusion by third parties listening to this conversation who are not in close proximity, because they will only hear Operator 1 and silence when Operator 2 transmits.
I often use this mode of communications when I discover a new repeater for which I do not know the access tone and I want to ask the Operator in close proximity to me for permission to use the Repeater and have him tell me the access tone.