Is it permissible for a guardian (Big brother) to unlawfully stop his sister from getting married?

If the guardian denies her right in getting married for an unlawful reason, she should go to court in order to settle that matter, and the guardian is considered sinful in this case.

Does Istigfar (Asking Allah for forgiveness) between the first and the second part of Friday prayer`s sermon render the prayer invalid?

Talking during Friday prayer`s sermon is disliked, but there is no harm in offering Istigfar between the two parts of the sermon, and it doesn`t invalidate the prayer as it is actually from Sunnah. And Allah Knows Best.

If a woman makes a vow to slaughter a sheep, and her husband is the one who buys it for her from his own money, and he says: "It is for you until you fulfill your vow with it," Is this permissible, or must she buy it herself from her own money?

If her husband gave her the sheep as a donation for the puprose of fulfilling the oath she made and was slaughtered by the wife or the husband on her behalf then the vow she made is fulfilled. And Allah Knows Best. 

What is the ruling on performing voluntary prayers during official working hours?

All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions

There is no harm if  there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.