There is no actual difference between rolling a 'd100' or rolling '2d10 with one tens die and one ones die', this goes for any dice, digital or real.
There IS a difference between rolling 1d12 vs 2d6, vs 3d4. This is because there are multiple ways to roll some results when using more that one die. Craps is a dice game built around '7' being the most common roll on 2d6.
Once you use a d10 for the tens place and a d10 for the ones place, this property no longer applies; there is only one combination of dice rolls that result in each number 1-100.
2d50 WOULD give the kind of center-skewed result you are describing, but of course then you couldn't roll a '1'!