The amount merchants are willing to pay depends on their Mercantile skill - the lower their skill, the more they'll pay, at least up to their maximum.
The most generous vendor - and not coincidentally the one with the lowest mercantile skill - is Sinderion in Skingrad, but he only has 400 septims and only buys and sells potions and ingredients and such.
Rohssan is actually not at all generous, and that's true of most of the vendors with the most money - they also have the highest Mercantile skill and thus pay the lowest prices. The merchant with the most money in the vanilla game is the fence Fathis Ules, and he's also a Mercantile master and extremely tight-fisted. Not to mention you have to be in the TG to deal with him.
The most generous vendor in the Market District is Rindir, though again, he doesn't have much money (only 600 septims). He does buy a pretty broad range of stuff though, and is far and away the merchant I deal with most often.
The best merchant in the vanilla game is Varel Morvayn at Morvayn's Peacemakers in Anvil. He has the best combination of high money and low mercantile skill, so he pays good prices and can afford to pay more (1200 septims).
Another notably good one is Daenlin at The Archer's Paradox in Bravil. He has fairly poor Mercantile skills and 1000 septims.
Most of the Mages Guild merchants are poorly skilled and thus generous, but they don't have much money and they usually only buy potions and ingredients and alchemy equipment.