This Wikipedia article mentions that the configuration space of a rolling ball is $\Bbb{C}^5$. I don't understand why that is.
The position of the center of mass, that's a point in $\Bbb{R}^3$. The axis and velocity of rotation, that's another point in $\Bbb{R}^3$ (this would give the orientation of the axis, the direction of rotation and also the velocity). Now we might also have a rate of change of axis. We may include as many derivatives with respect to time as we like. So we're essentially looking at $\Bbb{R}^{6+3d}$, where $d$ is the number of derivatives with respect to time of the change of axis that we take.
How can we be sure that the configuration space is exactly $\Bbb{C}^5$?
The configuration space is not $\mathbb{C}^5$. (And I don't see where in the Wikipedia article this is claimed.)
First: we are talking about a ball that is rolling on another ball. This means,
Thus the configuration space is $\mathbb{S}^2 \times SO(3)$ which has real dimension 5.
In terms of the group $G_2$, this is also not quite right. The correct description is found in this expository article: basically