Sorry for the late response, I didn't get an e-mail notification there was a reply.
As far as making the 3rd NIC work, I edited the "etc/rc.d/rc.local" to add a line similar to:
ifconfig eth2 172.x.x.x netmask 255.x.x.x broadcast 172.x.x.x
While I have not actually tested accessing shares, I was successfully able to ping from each Server to the other via those statics. I was waiting to get the other part (Directory Services, LDAP or NT4 Domain) working first.
That is a different range from the other two NICs (Local and Gateway). The 10GB NIC is directly attached (SFP Fiber) to the FreeNas Server which has a similar Static IP. ** When I say "Directly" I mean while the cards are physically attached, SME Server is a VM Instance on vSphere 5.5 Update 3 where I configured a separate Virtual Switch just for the 10 GB NIC (Full Disclosure

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AFAIK you don't need to enable LDAP auth to make FreeNas work..
True, but I want a single point of administration for Users and Groups and I believe to obtain this I would have to get Directory Services, NT4 Style or LDAP working between FreeNas and SME. Please correct me if I am wrong in this.
While the main purpose of connecting to FreeNas is to expedite the Backups (since they are taking so long now they are running into the next days start time); I would like to "off load" some other items to FreeNas:
1) Map User Directories to FreeNas instead so I can take advantage of "Snapshots" (Similar to MS "Shadow Copy")
2) Set Quotas
3) Easily expand shares/volumes
4) Leverage ZFS (Really RaidZ2)
5) Have the FreeNas Server backup the SME Backups and itself to a 3rd Storage (Will be the Drobo that it is replacing)
BTW, did I mention that the old SME Server will become an backup SME Server housed at a different location using AFFA?

AFAIK you don't need to enable LDAP auth to make FreeNas work..
anyway, if you enable it AFTER you restored your server, you'd not loose anything
This sounds promising, perhaps I will try to test it out with another VM instance running SME 8... Can't hurt
Hopefully I did not inundate you with too much information and thanks for your response.