Here is some more that were recently pointed out on King.net.
Adidas.tv
Mercedes-benz.tv
Boris-Becker.tv (OK not a brand but very famous and a stunning site)
EdFest.tv (World famous festival)
AT&T Williams F1 (Formula 1 team, i THINK F1 is most watched sport in the world so massive exposure)
Renault.tv
BMW-Web.tv (BMW's web TV channel)
Audi.tv
LittleBritain.tv (very famous TV show)
Supernatural.tv
VBS.tv
Ethical.tv
Green.tv
FTV.tv
G-star.tv
Vendr.tv
SingleMalt.tv
Pokerstars.tv
Partypoker.tv
Williamhill.tv
LiveScore.tv
HiltonHead.tv
Rawvegas.tv
PIC.tv
ABCNewsOne.tv
ZillionTV.tv
Stuff.tv................etc
Like Bob said, i would like to post a link but if i do so then they it will probably be my last post as apprently you cannot even acknowledge where you got info from now without a warning & a dirty look.

If you got the PM from Bob then you got the link i would of sent anyway.
Plenty of major brands using .tv these days, though many .tv owners don't appear to of noticed yet.