Chain derails on cassette when back-pedaling

I've got a new 10sp zee setup on my new bike, and I've set it up so that it all shifts correctly, but when I backpedal, the chain derails on the cassette. For example I've got it on the biggest sprocket, and it'll start to derail into the higher gears. Any ideas why? This is really irritating me.
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more so when everything is new.
Parktools :?:SheldonBrown
B'Twin Triban 5
B'Twin Triban 5
B'Twin Triban 5
Adjust the chainline and/or reduce the size of the largest rear cogs and/or front chainring.
yes having the chain line incorrect can result in that but it works both ways. bring it in and the chain "could" do the "same" on the "small" cogs.
but the most common issue is people just dont normally do this. and more so when they get a new bike but when they change to new kit they expect everything to work as it was before which it will not do. How would closer spacing do that? it has no effect on it. andthe cog is in the same place as the old one.
it just that it is new.
Parktools :?:SheldonBrown
Try it and see.
Think about it - the chainline is only ever going to be 'perfect' on one cog - whichever one it is the chain will naturally gravitate to that one.
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