Edit
The following code will select the word directly under the Mouse
Xaml
<TextBox MouseMove="TextBox_MouseMove"
         Text="Google(1) yahoo(2) apple(3) microsoft(4)"/>
Code behind
private void TextBox_MouseMove(object sender, MouseEventArgs e)
{
    TextBox textBox = sender as TextBox;
    Point mousePoint = Mouse.GetPosition(textBox);
    int charPosition = textBox.GetCharacterIndexFromPoint(mousePoint, true);
    if (charPosition > 0)
    {
        textBox.Focus();
        int index = 0;
        int i = 0;
        string[] strings = textBox.Text.Split(' ');
        while (index + strings[i].Length < charPosition && i < strings.Length)
        {
            index += strings[i++].Length + 1;
        }
        textBox.Select(index, strings[i].Length);
    }
}