A reservation is a promise, i.e. that while the memory might not be consumed / resident for the "reserver" right now, any allocation would be granted and if necessary forcefully taken away (reclaimed) from someone else. ESXi has a certain amount of default reservations for the purpose of stable operations, you are of course more likely to collide with those on a host that has as much memory as my phone.
The max you can reserve, is whatever is currently not reserved in the user pool (where the VMs go):
vsish -e get /sched/groups/4/stats/capacity | awk -F '[ :]' '$4 ~ /mem-unreserved/ {print $5/1024" MB"}'
Note that you _shouldn't_ reserve all of that in any environment that you care about because under some circumstances ESXi might need to reserve more (e.g. heavy IO workloads) and if it can't, will PSOD.
To list all current reservations > 9 MB:
memstats -r group-stats -s gid:name:min:conResv:availResv:memSize -u mb | sed -n '/^-\+/,/.*\n/p' | awk 'NR == 3 || length($3) !~ 1 {print $0}'
any form of passthrough requires memoy preallocation (since 6.5) which in turn requires a full reservation.