Solution
The option to switch PLL modes is a native function of USRP Hardware Driver™ (UHD) which is what GNU Radio operates on. While the NI-USRP and NI USRP RIO drivers do have some UHD components, most of it is custom code and is wrapped around UHD, thus not offering the same functionality.
This parameter cannot be changed within the LabVIEW environment as it runs the NI-USRP, and USRP RIO FPGA drivers, and not the Ettus UHD driver.