Do like suggested above, either import the vcenter SSL Certs or disable the SSL
To disable SSL Certificate Validation, run the following script: /etc/wemi/utils/disable_ssl_validation.sh.
Did you create \\server\share? I don't think AV3 will create it for you. I have successfully "configured" file shares. I created them on the file server first then in AV3 I was able to add them straight away.
(Not that I am home free. Haven't successfully got an app assigned and working yet.)
We had the same issue over here when we had ldap set to use ssl. Either turning ssl off or enabling ssl in the old management interface on port 3443 solved the problem for us.