WPF TabItem Header Styling

Try this style instead, it modifies the template itself. In there you can change everything you need to transparent:

<Style TargetType="{x:Type TabItem}">
  <Setter Property="Template">
    <Setter.Value>
      <ControlTemplate TargetType="{x:Type TabItem}">
        <Grid>
          <Border Name="Border" Margin="0,0,0,0" Background="Transparent"
                  BorderBrush="Black" BorderThickness="1,1,1,1" CornerRadius="5">
            <ContentPresenter x:Name="ContentSite" VerticalAlignment="Center"
                              HorizontalAlignment="Center"
                              ContentSource="Header" Margin="12,2,12,2"
                              RecognizesAccessKey="True">
              <ContentPresenter.LayoutTransform>
            <RotateTransform Angle="270" />
          </ContentPresenter.LayoutTransform>
        </ContentPresenter>
          </Border>
        </Grid>
        <ControlTemplate.Triggers>
          <Trigger Property="IsSelected" Value="True">
            <Setter Property="Panel.ZIndex" Value="100" />
            <Setter TargetName="Border" Property="Background" Value="Red" />
            <Setter TargetName="Border" Property="BorderThickness" Value="1,1,1,0" />
          </Trigger>
          <Trigger Property="IsEnabled" Value="False">
            <Setter TargetName="Border" Property="Background" Value="DarkRed" />
            <Setter TargetName="Border" Property="BorderBrush" Value="Black" />
            <Setter Property="Foreground" Value="DarkGray" />
          </Trigger>
        </ControlTemplate.Triggers>
      </ControlTemplate>
    </Setter.Value>
  </Setter>
</Style>