Real simple answers.
Q) Is Shard of Contempt an upgrade over -
A) Yes. Yes it is.
Q) But you didn't even let me finish!
A) I don't need to. If you have to ask, it's a goddamn upgrade.
Q) Is there any way it's not an upgrade?
A) I can think of two situations in which Shard of Contempt is not a clear upgrade.
1: You have Blackened Naaru Sliver/Dragonspine Trophy, in which case, you really shouldn't need to ask this question and this thread is not for you. I hope to god you don't need to ask that question.
2) You're already Expertise capped, in which case, you should replace your Vashj belt/Hydross shoulders/terrible Alar gloves with better, non-expertise stuff and equip a friggin Shard.
Q) What if I'm Mutilate/Shadowstep/Hemo?
A) Still better. In fact, if you're Mutilate, it's probably better than DST. Shard/Ashtongue is disgusting.
Q) I don't understand Expertise.
A) Okay, you know those annoying dodges? The ones that reduce your DPS and won't go away no matter how many Rigid Dawnstones you put in everything? Expertise makes those go away - not just on your white damage, but on your specials (which is why the Shard is so sickeningly good for Mutilate.) Until you cap it out (at 103 rating, 63 if you're combat, 43 if you're human), Expertise is god damn amazing. It's hit rating on crack. It's old-school Weapon Skill with a side of good itemization. It's Karl Malone driving across the court and dunking in five guys' face without spilling the beer in his other hand. It's the pimpest *@%* there is.
Q) What about the proc?
A) 10%-ish proc rate, 20-second duration, 45-second hidden cooldown. So that's pretty much nearly a 50% uptime rate for 230 AP. So yeah the proc is amazing, and that's why this isn't a gimmicky "let's cap Expertise and stand in the frontal arc of anything that doesn't cleave!" item. It's just a winner and if you see one drop, stab the rest of your group to equip it.
Q) Is this useful for anyone else?
A) DPS warriors, bonkadins, Enhance shammies, and feral druids can all get some good use out of it, especially the latter two with their lack of Expertise talents. You should still stab them if they outroll you on it, but that's just to make sure you get it, not on any sort of principle. It's not a DST.
But for the love of God, don't let a hunter take it.
Q) So why don't you have one?
Shut the hell up.