They cannot, under the Constitution. Of course, at the point the National Guard is being mobilized to prevent actions of the federal government, we are deep into a constitutional crisis and a short distance from a (possibly very brief) active civil war.
> A quick read on Wikipedia points to the Constitution saying it would take Congress for the federal government to take command unilaterally.
Congress has already done so , setting rules which require only a Presidential determination to invoke [0], and Presidents have used the authority so granted specifically to deal with very much the same state rebellion scenario you suggest, notably Eisenhower in 1957 when the Arkansas National Guard was deployed to prevent the implementation of a federal court order integrating Central High School in Little Rock: Eisenhower did the one-two punch of federalizing the entire Arkansas National Guard, ordered them away, and also deployed the Army (101st Airborne) to enforce the order. [1]
[0] in the Insurrection Act; the specific relevant provision is at 10 USC § 252: “Whenever the President considers that unlawful obstructions, combinations, or assemblages, or rebellion against the authority of the United States, make it impracticable to enforce the laws of the United States in any State by the ordinary course of judicial proceedings, he may call into Federal service such of the militia of any State, and use such of the armed forces, as he considers necessary to enforce those laws or to suppress the rebellion.” (emphasis added)
