You cannot pass through the PCI device to the virtual machine as a PCI device. Now, if you have the drivers in your host OS to recognize the PCI device, and see the serial port(s) it uses, you should be able to assign the host's serial port to the virtual machine. If you didn't have the device into the PC when you installed VMware Workstation, then the vmserial driver probably did not get installed. With the PCI card inserted, re-run the Workstation setup in maintenance mode, and the vmserial driver *should* get installed - and then you should be able to assign that COM port to your guest and use it.
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