The IsMouseOver and IsPressed brushes are hardcoded into the default ControlTemplate for the Button.
You could copy the default template into your XAML markup by right-clicking on the Button element in design mode in Visual Studio or in Blend and choose Edit Template->Edit a Copy.
You would then edit the template as per your requirements:
<Style x:Key="PanelButtonStyle" TargetType="Button" BasedOn="{StaticResource {x:Type Button}}">
<Style.Resources>
<Style x:Key="FocusVisual">
<Setter Property="Control.Template">
<Setter.Value>
<ControlTemplate>
<Rectangle Margin="2" SnapsToDevicePixels="true" Stroke="{DynamicResource {x:Static SystemColors.ControlTextBrushKey}}" StrokeThickness="1" StrokeDashArray="1 2"/>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
<SolidColorBrush x:Key="Button.MouseOver.Background" Color="#479DE0"/>
<SolidColorBrush x:Key="Button.MouseOver.Border" Color="#FF3C7FB1"/>
<SolidColorBrush x:Key="Button.Pressed.Background" Color="#FFC4E5F6"/>
<SolidColorBrush x:Key="Button.Pressed.Border" Color="#FF2C628B"/>
<SolidColorBrush x:Key="Button.Disabled.Background" Color="#FFF4F4F4"/>
<SolidColorBrush x:Key="Button.Disabled.Border" Color="#FFADB2B5"/>
<SolidColorBrush x:Key="Button.Disabled.Foreground" Color="#FF838383"/>
</Style.Resources>
<Setter Property="Background" Value="Purple" />
<Setter Property="Template">
<Setter.Value>
<ControlTemplate TargetType="{x:Type Button}">
<Border x:Name="border" BorderBrush="{TemplateBinding BorderBrush}" BorderThickness="{TemplateBinding BorderThickness}" Background="{TemplateBinding Background}" SnapsToDevicePixels="true">
<ContentPresenter x:Name="contentPresenter" Focusable="False" HorizontalAlignment="{TemplateBinding HorizontalContentAlignment}" Margin="{TemplateBinding Padding}" RecognizesAccessKey="True" SnapsToDevicePixels="{TemplateBinding SnapsToDevicePixels}" VerticalAlignment="{TemplateBinding VerticalContentAlignment}"/>
</Border>
<ControlTemplate.Triggers>
<Trigger Property="IsDefaulted" Value="true">
<Setter Property="BorderBrush" TargetName="border" Value="{DynamicResource {x:Static SystemColors.HighlightBrushKey}}"/>
</Trigger>
<Trigger Property="IsMouseOver" Value="true">
<Setter Property="Background" TargetName="border" Value="{StaticResource Button.MouseOver.Background}"/>
<Setter Property="BorderBrush" TargetName="border" Value="{StaticResource Button.MouseOver.Border}"/>
</Trigger>
<Trigger Property="IsPressed" Value="true">
<Setter Property="Background" TargetName="border" Value="{StaticResource Button.Pressed.Background}"/>
<Setter Property="BorderBrush" TargetName="border" Value="{StaticResource Button.Pressed.Border}"/>
</Trigger>
<Trigger Property="IsEnabled" Value="false">
<Setter Property="Background" TargetName="border" Value="{StaticResource Button.Disabled.Background}"/>
<Setter Property="BorderBrush" TargetName="border" Value="{StaticResource Button.Disabled.Border}"/>
<Setter Property="TextElement.Foreground" TargetName="contentPresenter" Value="{StaticResource Button.Disabled.Foreground}"/>
</Trigger>
</ControlTemplate.Triggers>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
Just adding triggers to the Style without modifying the template won't work because of how the default template is defined.