There were several NOPs - XCHG BX,BX and so on. Those were taken later to be prefixes for new classes of opcodes.
You're probably confusing with:
- POP CS being broken and later becoming a prefix
- some opcodes being "reserved NOPs", i.e. reserved without generating #UD. They are used for instructions that may be defined in the future while guaranteeing backwards compatibility, for example new kinds of prefetches. MPX bounds checking instructions were also encoded in reserved NOPs.
It's interesting that a lot of ALU operations occupy four opcodes (memory source/memory destination x byte/word) but 0x84/0x85 and 0x86/0x87 only need two because not only are they commutative, but also 0x84/0x85 do not write to any operands and 0x86/0x87 write to both. So there is no difference between memory as the source or destination operand.