Just a note - to claim the spousal tax credit for a non-resident spouse, you will have to demonstrate that you're supporting your spouse (e.g. evidence of transfer payments). Support is defined as helping meet his/her basic needs.
Unless your spouse is filing a return or applying for a credit, she won't actually need a temporary SIN.
If you did want to get her one, here's the form: http://www.cra-arc.gc.ca/E/pbg/tf/t1261/t1261-12e.pdf