Lamara Bell, 25, and 28-year-old John Yuill were on the M9 when the crash took place – but it allegedly took two reports before officers attended the scene.
John tragically died as a result of the accident on Wednesday, while Lamara was left with serious injuries.
In a statement, Assistant Chief Constable Kate Thomson said: "Police Scotland were called to the M9 southbound near junction 9 at around 9.50am on Wednesday morning following reports of a one car road traffic collision involving a Renault Clio which had left the road.
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"Officers attended and the male driver of the car was sadly pronounced dead at the scene. The female passenger was conveyed to the Southern Gerneral, Glasgow, where she is in a critical condition.
"We believe that this is connected to the ongoing missing persons search for John Yuill, 28, and Lamara Bell, 25."
The statement confirmed that, 'for reasons currently being investigated', police did not attend the scene of the crash when it was first reported.
"A call was made to police late on Sunday morning regarding a car which was reported as being off the road […] That report was not followed up at the time," Kate Thomson added.