First, you should always take advantage of a unicorn situation. You don't want to be left wondering what-if ten and twenty years down the road.

In getting this set up, your word choice can help lubricate the gears:
referring to her as your better half and your reason for living, e.g..

One point to help put both women at ease is to tell them in advance that any recordings would be on their phones, not yours. This also gives them time to request or order a mask. (Lace hoods are kinda classy, fwiw.) That she could have video evidence for divorce court if you're too attentive to the coworker may help assure her further. Or wear a mask.

To further assure her, you can make it all about her permission. She makes the arrangements. And once you're together, she plays the role of porn film director, telling you what to do to the coworker. So every step of the way is with her permission. You can add some edge by announcing a rule once your guest has arrived that whatever your wife says goes, but after you've done it, if either you or the coworker thought it was going too far, either of you get to tell the wife what she has to do to your coworker. It maintains mutuality and encourages escalation while ensuring everything your wife wanted to see comes to fruition.

Plan in advance some positions that have you fucking the coworker but your lips on your wife, e.g., the double down. The BJ switch is a MMF position that can be gender-reversed. (No name for the FFM version that I could find.)

Another step to assure your wife is to dress her before the guest arrives in a type of lingerie you've always wanted to see her in. In other words, ensure she's the best-dressed woman in the house. Give her the spa treatment before dressing her up, e.g., shave her kitty super smooth.

To further assure your wife, you can turn the tables after you've started and make it about HER getting fucked, depending on how into the coworker your wife is. (She did the picking, after all.) You may want to have some new equipment hidden nearby to give them encouragement, like a strap-on for the coworker to wear so the two of you can spitroast your wife; a double-headed dildo; or a double ball gag. You may or may not need to give them guidance in getting into position with the double-ended dildo, so your secretly learning some positions in advance could improve your persuasiveness: butt bumping, reclining (scissors), toy-sharing, the butterchurner, and reverse-cowgirl on a Viennese oyster (brute position). You may want a wand ready for the toy-sharing position, or you may decide to slide yourself under the action, to kiss up to your wife some more.

tl;dr: yes