Something I truly miss from Android is its possibilities with Tasker.
IOS with its restrictions to the underlaying OS and components make it more secure, but less available (ref. Confidentiality, Integrity, Availability).

IOS has a less powerful tool similar to Tasker; Shortcuts. With that tool I have made some simple automations pausing or muting media when calling out (and starting media when call has ended) with the help of Webhooks.
It only works with outgoing calls since it triggers on opening the Phone app. Incoming calls are integrated part of IOS and is not accessible through Shortcuts.
I recommend using Webhooks only on a non public Home Assistant setup and with less critical entities (media, lights etc), since it controls through http POST commands without authentication.

Shortcuts settings (open Phone app):

The url is in the format https://homeassistanturl/api/webhook/phonecallpausemutemediaxxx

Automation:

# Phone call finished - play or unmute audio
- alias: Phone call finished play or unmute media
  id: phone_call_finished_play_unmute_media
  trigger:
  - platform: webhook
    webhook_id: "phonecallfinishedxxx"
  condition:
    condition: and
    conditions:
    - condition: state
      entity_id: group.all_people
      state: 'home'
  action:
  - service: media_player.volume_mute
    data:
      is_volume_muted: false
    target:
      entity_id: media_player.kitchen_radio
  - service: media_player.media_play
    target:
      entity_id: media_player.mediacenter

# Phone call - pause or mute media
- alias: Phone call pause or mute media
  id: phone_call_pause_mute_media
  trigger:
  - platform: webhook
    webhook_id: "phonecallpausemutemediaxxx"
  condition:
    condition: and
    conditions:
    - condition: state
      entity_id: group.all_people
      state: 'home'
  action:
  - service: media_player.volume_mute
    data:
      is_volume_muted: true
    target:
      entity_id: media_player.kitchen_radio
  - service: media_player.media_pause
    target:
      entity_id: media_player.mediacenter