I might be in the minority posting here, but the trouble I have consistently had with Time Out is just this: getting a child to sit through it without more drama. As a preschool teacher, it took me (too many!) years to realize that this One-Size Fits All method of punishment wasn't working for me effectively with the children that needed it most.
The first challenge is that the Time Out punishment is virtually unrelated to the action we are trying to curb in the first place. "You hit someone so now go sit" works okay with more docile children, but children who are really needing to cool off and understand/work through their feelings constructively get very sidetracked by Time Out. It does nothing to promote the parent taking a moment to check in with the child and do a little detective work: what's going on with the child that they are doing something that is destructive, hurtful or otherwise unproductive? Acting out behaviors don't exist in a vacuum and there are nearly always underlying reasons, often reasons of which the child is unaware.
What has worked very well for me is drop the idea that each negative action has to be handled in the exact same way. We talk a lot about consistency as parents, but our children sometimes respond (I say sometimes, each child is different) to direction more tailored to the situation.
In cases where a child is resistant to following a simple direction; I may need to reflect and see if they are resisting because they are really in fact wanting my help and companionship or if there's something else going on. A child who is digging their heels in and not going to budge may be asked to sit in an out-of-the-way place until *they* are ready to do as they are asked. This may take the child one minute or ten minutes: the difference is that they make the choice on when they are ready to comply. When they return and follow through on the task, I let it go without further conversation other than a simple "thank you". If they return and are not ready to follow through, I bring them back to their seat and say something equally simple :"I see that you aren't ready to do XYZ, and so I need you to sit down until you are ready." And then, yes, I return them again and again always with the invitation to return when they are ready.
Giving children control over being able to fix a problem in their own time has been wonderful. What I've seen is that some children needed to sit by themselves for half a second before complying, while others take longer. Sometimes, much longer. What I realize in those other instances is that the child felt that they needed a break from the goings-on of the day and while this wasn't the best way for them to go about it, now that they have been given a safe space to do so, they've got a chance to relax and get their bearings. If allowed to return on their own in their own time, most children are happier coming back.
I suspect that this is because children lack the self-awareness to identify that they need to take a break from the action and usually find ways of expressing their sense of stress and agitation by acting out. So,for many kids, a 2 or 3 minute time out really isn't enough time for them to get it together and come back successfully. Also, because Time Out is often a punishment that is meted out before any problem-solving has occured (go sit, and then we'll talk). For some children, they are further angered because not only is their problem not solved, they are being punished for an action that may have stemmed from other circumstances.
In other cases, and especially with older kids, simply stating what you see and asking them to head to their rooms until they are ready to be safe or follow directions really helps. Yes, they will likely play in their room, but this isn't a reward: the child generally wants to feel included but may also need a break. I've used this well esp. after school with older kids, when they may need a break from the all the adult direction they've received previously. With the older kids,if they haven't emerged in a half-hour, I go and just check in: ask when they plan on doing their homework or other necessary tasks, or we can make a plan so that they are able to solve any problems that they were dealing with before they went to their room.
In my experience, allowing children to figure out how much time they need alone has been empowering for both the children and myself. Instead of trying to make a punishment work the same way for each kid, I give them a concrete message that I want to help them be able to be in the group, but it's up to them as to when they want to do it. Kids need breaks far more often than we realize; we adults rarely take good-enough care of ourselves to make ourselves take breaks when we need to, so some days we can be even less clued in as to what our kids need, and the intensity of asking them to figure it out ("Do you need a break?" which can sound like more of a threat than an invitation)--this intensity may be more than an upset child can manage.
So, long suggestion short, see if you can modify your child's time away from the action and try it for a while. It takes kids a little time to learn new skills and this is a big one. Self-regulation is hard, hard work for children, most especially when they are frustrated with a person or a thing. (Maybe the toy wasn't working correctly, and that's the reason they threw it--that sort of thinking.) You can still have clear limits while helping the children learn how to manage themselves bit by bit. I also noticed that when I started using this technique, my relationships with the children improved because we weren't butting heads on a regular basis. It helped the children grow a little, too, I think.