What you're seeing is the is a bit of legacy code showing it's head.
At the heart of the matter is the VT_BOOL type. VB6 used the VT_BOOL type (aka VARIANT_BOOL) for its boolean values. True for a VARIANT_BOOL is represented with the value VARIANT_TRUE which has the integer value -1. During the conversion to .Net it was decided that when using VB conversion routines to convert a boolean value to an Integer value, VB6 semantics would be maintained an the return value would be -1.
The first implicit conversion occurs with the b = i line. Under the hood this does an implicit conversion from integer to boolean. Any non-zero value is deemed to be true therefore the resulting value is true.
However, the following line of code is doing an implicit conversion to an integer type.
i = b
Under the hood this uses one of the VB conversion routines (CType or CInt) to convert the value to an integer. As such VB semantics are in play and the value returned is -1.
The next interesting line is Convert.ToInt32() line. This is using a .Net conversion routine which does not use VB semantics. Instead in returns the underlying BCL representation for a true boolean value which is 1.