reserve accounts at the central bank are important to understand the mechanics of how asset purchase happens. generally speaking, if an institution has an account at the central bank - reserve or other deposit account, they will use it whenever possible to settle payment
also note that it's not just commercial banks that have accounts at the central bank. it varies by jurisdiction, but other entities also have accounts at the central bank for example, in the US the Treasury has an account at the Fed - the Treasury General Account (TGA)