No, there is no reason to do a greenfield VMS deployment and hasn't been for a long time.
> I've heard its reliability is legendary, but I've never tried it myself.
I've heard the same things but I am doubtful as to their veracity in a modern context. Those claims sound like they come from an era where VMS was still a cutting-edge and competitive product. I'm sure VMS on vaxclusters had impressive reliability in the 1980s, but I doubt it's anything special today. If you look at the companies and institutions that need performance and high reliability today (e.g. Hyperscaler companies or the TOP500) they are all using the same thing: Linux on clusters of x86-64 machines.
They are completely different mental models and ways of thinking about the problem of reliability and uptime.
VMS(and IBM/360 and other large compute systems) will almost certainly give you stronger uptime guarantees than any modern compute stack, but almost nobody needs uptimes measured in literal decades.
The Hyperscaler/TOP500 computing needs are not optimized for reliability in the same ways OpenVMS does.