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Read Article I, clauses 8 & 9 sometime. They are very enlightening, I assure you, as to the powers specifically reserved to the federal government.

Article 1, Section 8, Clause 1 - taxes and imposts. Nothing there to prohibit secession.
Article 1, Section 8, Clause 2 - borrow money. Ditto.
Article 1, Section 8, Clause 3 - commerce. Ditto.
Article 1, Section 8, Clause 4 - naturalization, bankruptcy. Ditto.
Article 1, Section 8, Clause 5 - coin monies, weights & measures. Ditto.
Article 1, Section 8, Clause 6 - counterfeiting. Ditto.
Article 1, Section 8, Clause 7 - Post offices & post roads. Ditto.
Article 1, Section 8, Clause 8 - Arts & sciences, copyrigthts and patents. Ditto.
Article 1, Section 8, Clause 9 - court system. Ditto.
Article 1, Section 8, Clause 10 - piracies, international offenses. Ditto.
Article 1, Section 8, Clause 11 - declare war, marques & reprisals, captures. Ditto.
Article 1, Section 8, Clause 12 - armies. Ditto.
Article 1, Section 8, Clause 13 - navies. Ditto.
Article 1, Section 8, Clause 14 - military regulations. Ditto.
Article 1, Section 8, Clause 15 - call militia, insurrections and invasions. Ditto.
Article 1, Section 8, Clause 16 - orgainize and control militia. Ditto.
Article 1, Section 8, Clause 17 - seat of government, purchased federal property. Ditto.
Article 1, Section 8, Clause 18 - enact legislation for foregoing powers. Ditto.

Article 1, Section 9, Clause 1 - slave trade. Ditto.
Article 1, Section 9, Clause 2 - suspend Writ of Habeas Corpus. Ditto.
Article 1, Section 9, Clause 3 - no Bill of Attainder or ex post facto law. Ditto.
Article 1, Section 9, Clause 4 - no direct tax. Ditto.
Article 1, Section 9, Clause 5 - no tax on exports. Ditto.
Article 1, Section 9, Clause 6 - commercial preferences, no duties. Ditto.
Article 1, Section 9, Clause 7 - appropriations made by law. Ditto.
Article 1, Section 9, Clause 8 - no titles of nobility.

Those are the powers specifically reserved to the federal government. And what do you know, secession is prohibited. < /sarcasm >

My bad.

Article 1, Section 9, Clause 8 - no titles of nobility. Ditto.

Ohoh, you are doing a railsplit and ignoring Article I, section 10 - you know, the one which limits the powers of the individual states.

You will note that the state governments can't exercise these powers. If they try to, it goes against the supremacy clause. By seceding, the states are asserting that the supremacy clause is null and void, since they are making a law which is superior to the constitution. Not to mention the fact that they are also asserting a sovereignty not granted them under the constitution.