The application is home theater, consumer 5.1 surround sound. You are also adding DSP active 2-way crossovers to the front left and front right. This is not 7.1 surround.
You are already using the RME HDSP 9632, which gets you RME's excellent drivers. And you have added the RME AO4S-192 expansion card, for a current total of six channels of analog output.
While I certainly advocate RME's excellent products, I do not think that you will make good use of premium DA conversion on subwoofers and on home theater rear surround satellite loudspeakers. For this application, I would suggest increasing channel count by adding a (roughly $200) Behringer ADA8200 eight channel ADAT connected AD/DA converter. Avoid the older ADA8000.
Use the excellent RME DA converters (that you already have) to feed the front loudspeakers. That includes the front center, front left, front right, and the two bass bins added by the DSP active 2-way crossovers. That is five channels from the available six, leaving one spare. Maybe later you can use that one spare channel to add woofers to the front center.
Use that ADA8200 for the rear left and rear right surround channels, and for the LFE (low frequency effects) subwoofer channel. That is using three channels from the available eight, leaving five spares. Later you might use it to add more surround channels and/or to add more individually equalized subwoofer channels, or maybe add some tactile transducers. According to a review at Sound on Sound, the measured high pass corner frequency on the ADA8200 is -3_dB at 6_Hz, well suited to use with the LFE.
Route the digital audio with TotalMix. Maybe use TotalMix Remote to remotely activate/deactivate mute and adjust level.