There is a comprehensive article on the Windows OS Hub that discusses administrative shares and how they can be tricky to access in a non-domain environment. I needed to run psexec against a standalone machine and the solution for that was to add an entry to the registry on the target machine.
Open Registry Editor (regedit.exe)
Go to HKEY_LOCAL_MACHINE\SOFTWARE\Microsoft\Windows\CurrentVersion\Policies\System
Create a new DWORD (32-bit) parameter with the name LocalAccountTokenFilterPolicy
Set the LocalAccountTokenFilterPolicy parameter value equal to 1
Restart the computer to apply the changes
