I had black stuff deposited on shoulders of .204 R cases. Soot was also deposited on bolt face. Looking at the problem showed the cases needed to be trimmed. Apparently, jamming the mouth of the case against the front end of the chamber prevented complete neck expansion. Trimming the cases fixed the soot situation.
More likely, as mentioned, sounds like neck work hardening. Inadequate seal between neck & chamber, bullet kicked into throat without adequate neck tension caused by work hardening (brass spring back) followed by backed up gas/crud deposition on shoulder. - "It didn't do this with virgin brass at much milder loads". With velocites in excess of 3,000 with 109's sounds like pressures are close to max, like 60K plus. New brass (wirgin brass) would be shorter than multi-fired brass. Possibly brass length to chamber might be worth checking. Annealing makes for nice soft clingy brass (large crystal size) needed for consistent neck tension.
I should be so fortunate to have: "I have about 12lbs of h4350 that I've got to use."
I shoot real cheap, once fired Federal 6.5 CM brass necked down to 6mm CM, turned to .268 with 42.0 gr. AA4350 & Barnes 105 Match Burners & CCI 41 primers. Cases turned to 1.91. Soot & crud now appearing on shoulders so I will anneal & trim to 1.91. Best accuracy sort of (but not quite) approaches that of OP, 3 bullets in same hole. Neck tension approx same as OP's.