With all due respect, try reading the instruction manual.
19. Digital Connections
19.1 ADAT
The ADAT optical I/O of the HDSPe AIO Pro is fully compatible to all ADAT equipped units. RME's unsurpassed Bitclock PLL prevents clicks and drop outs even in extreme varipitch operation, and guarantees a lightning fast, yet low jitter and sample accurate lock to the digital input signal. A usual TOSLINK cable is sufficient for connection.
ADAT In
Interface for a device sending an ADAT signal to the HDSPe AIO Pro. Carries the channels 1 to 8. When receiving a Double Speed signal this input carries the channels 1 to 4, at Quad Speed channels 1 and 2. Can also be used as SPDIF optical input.
ADAT Out
Interface for a device receiving an ADAT signal from the HDSPe AIO Pro. Transmits channels 1 to 8. When sending a Double Speed signal, this port carries channels 1 to 4, with Quad Speed channels 1 and 2. Can also be used as SPDIF optical output.
I’m unfamiliar with the RME PCIe cards but my reading is that the ADAT connections are dual purpose optical for ADAT and SPDIF.
Try connecting the Octapre out to the RME via ADAT out on the OctaPre to ADAT in on the RME and select RME as master clock.
Hopefully someone clever than me will validate this or correct it!