The two colors may not look close, but there are only 140 "named" colors out of 16,777,216 possible combinations (256 * 256 * 256).
It is difficult to look at the RGB values and make any conclusions regarding the color matching.
'GetNearest...
'   http://social.msdn.microsoft.com/Forums/en-US/vbgeneral/thread/b2d491ac-4031-46d6-bccb-8bf9a46c2289
'   http://www.eggheadcafe.com/conversation.aspx?messageid=31472401&threadid=31472286
Imports System.Drawing
Imports System.Reflection
Imports System.Runtime.CompilerServices
Namespace Drawing
    <HideModuleName()> _
    Public Module ColorExtensions
        ''' <summary>
        ''' Gets the <see cref="System.Drawing.Color.Name">System.Drawing.Color.Name</see> of the closest matching color.
        ''' </summary>
        ''' <example>
        ''' <code>
        '''    Private Sub Example()
        '''        Dim oColor As Color = Color.FromName(GetNearestName(Color.FromArgb(255, 255, 255, 0)))
        '''        Debug.Assert(oColor.Name = "Yellow")
        '''    End Sub
        ''' </code>
        ''' </example>
        <Extension()> _
        Public Function GetNearestName(ByVal unknownColor As Color) As String
            'short-circut
            If unknownColor.IsNamedColor Then
                Return unknownColor.Name
            End If
            Dim oBestMatch As ColorName = GetNearestNameInternal(unknownColor)
            Return oBestMatch.Name
        End Function
        ''' <summary>
        ''' Gets the <see cref="System.Drawing.KnownColor">System.Drawing.KnownColor</see> of the closest matching known color.
        ''' </summary>
        ''' <example>
        ''' <code>
        '''    Private Sub Example()
        '''        Dim oColor As Color =  Color.FromKnownColor(GetNearestKnownColor(Color.FromArgb(255, 255, 255, 0)))
        '''        Debug.Assert(oColor.Name = "Yellow")
        '''    End Sub
        ''' </code>
        ''' </example>
        <Extension()> _
        Public Function GetNearestKnownColor(ByVal unknownColor As Color) As KnownColor
            'short-circut
            If unknownColor.IsKnownColor Then
                Return unknownColor.ToKnownColor
            End If
            Dim oBestMatch As ColorName = GetNearestKnownColorInternal(unknownColor)
            Return oBestMatch.Color.ToKnownColor
        End Function
        <DebuggerDisplay("Name={Color.Name}, Distance={Distance}, ARGB=({Color.A}, {Color.R}, {Color.G}, {Color.B})")> _
        Friend Structure ColorName
            Public Name As String
            Public Color As Color
            Public Distance As Double
            ''' <summary>
            ''' Returns RGB=(212,208,200)
            ''' </summary>
            Public Function ToRGBString() As String
                Return String.Format("RGB=({0},{1},{2})", Color.R, Color.G, Color.B)
            End Function
        End Structure
        Friend Function GetNearestNameInternal(ByVal unknownColor As Color) As ColorName
            Dim oBestMatch As ColorName = Nothing
            Dim nClosestDistance As Double = Double.MaxValue
            Dim oBindingFlags As BindingFlags = _
                BindingFlags.DeclaredOnly Or _
                BindingFlags.Public Or _
                BindingFlags.Static
            For Each oProperty As PropertyInfo In GetType(Color).GetProperties(oBindingFlags)
                Dim oNamedColor As Color = DirectCast(oProperty.GetValue(Nothing, Nothing), Color)
                Dim nDistance As Double
                nDistance = System.Math.Sqrt( _
                    (CInt(unknownColor.R) - oNamedColor.R) ^ 2 + _
                    (CInt(unknownColor.G) - oNamedColor.G) ^ 2 + _
                    (CInt(unknownColor.B) - oNamedColor.B) ^ 2)
                nDistance = System.Math.Sqrt(nDistance / 3)
                If nDistance < nClosestDistance Then
                    nClosestDistance = nDistance
                    oBestMatch.Name = oProperty.Name
                    oBestMatch.Distance = nDistance
                    oBestMatch.Color = oNamedColor
                End If
            Next
            Return oBestMatch
        End Function
        Friend Function GetNearestKnownColorInternal(ByVal unknownColor As Color) As ColorName
            Dim oBestMatch As ColorName = Nothing
            Dim nClosestDistance As Double = Double.MaxValue
            For Each sColorName As String In [Enum].GetNames(GetType(KnownColor))
                Dim oNamedColor As Color = Color.FromName(sColorName)
                Dim nDistance As Double
                nDistance = System.Math.Sqrt( _
                    (CInt(unknownColor.R) - oNamedColor.R) ^ 2 + _
                    (CInt(unknownColor.G) - oNamedColor.G) ^ 2 + _
                    (CInt(unknownColor.B) - oNamedColor.B) ^ 2)
                nDistance = System.Math.Sqrt(nDistance / 3)
                If nDistance < nClosestDistance Then
                    nClosestDistance = nDistance
                    oBestMatch.Name = oNamedColor.Name
                    oBestMatch.Distance = nDistance
                    oBestMatch.Color = oNamedColor
                End If
            Next
            Return oBestMatch
        End Function
#Region " Conditional Testing for GetNearest... Methods "
        <Conditional("DEBUG")> _
        Friend Sub TestGetNearest()
            'from immediate window
            '   ColorExtensions.Test
            '
            'Results based on "Windows XP" default theme, with the display name of "Windows XP style'.
            '
            'Windows XP style
            '   ActiveBorder, RGB=(212,208,200); LightGray, RGB=(211,211,211); ActiveBorder, RGB=(212,208,200)
            '   ActiveCaption, RGB=(0,84,227); RoyalBlue, RGB=(65,105,225); ActiveCaption, RGB=(0,84,227)
            '   ActiveCaptionText, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   AppWorkspace, RGB=(128,128,128); Gray, RGB=(128,128,128); AppWorkspace, RGB=(128,128,128)
            '   Control, RGB=(236,233,216); AntiqueWhite, RGB=(250,235,215); Control, RGB=(236,233,216)
            '   ControlDark, RGB=(172,168,153); DarkGray, RGB=(169,169,169); ControlDark, RGB=(172,168,153)
            '   ControlDarkDark, RGB=(113,111,100); DimGray, RGB=(105,105,105); ControlDarkDark, RGB=(113,111,100)
            '   ControlLight, RGB=(241,239,226); Beige, RGB=(245,245,220); ControlLight, RGB=(241,239,226)
            '   ControlLightLight, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   ControlText, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   Desktop, RGB=(0,78,152); Teal, RGB=(0,128,128); Desktop, RGB=(0,78,152)
            '   GrayText, RGB=(172,168,153); DarkGray, RGB=(169,169,169); ControlDark, RGB=(172,168,153)
            '   Highlight, RGB=(49,106,197); RoyalBlue, RGB=(65,105,225); Highlight, RGB=(49,106,197)
            '   HighlightText, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   HotTrack, RGB=(0,0,128); Navy, RGB=(0,0,128); HotTrack, RGB=(0,0,128)
            '   InactiveBorder, RGB=(212,208,200); LightGray, RGB=(211,211,211); ActiveBorder, RGB=(212,208,200)
            '   InactiveCaption, RGB=(122,150,223); CornflowerBlue, RGB=(100,149,237); InactiveCaption, RGB=(122,150,223)
            '   InactiveCaptionText, RGB=(216,228,248); Lavender, RGB=(230,230,250); InactiveCaptionText, RGB=(216,228,248)
            '   Info, RGB=(255,255,225); LightYellow, RGB=(255,255,224); Info, RGB=(255,255,225)
            '   InfoText, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   Menu, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   MenuText, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   ScrollBar, RGB=(212,208,200); LightGray, RGB=(211,211,211); ActiveBorder, RGB=(212,208,200)
            '   Window, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   WindowFrame, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   WindowText, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   Transparent, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   Black, RGB=(0,0,0); Black, RGB=(0,0,0); ControlText, RGB=(0,0,0)
            '   Gray, RGB=(128,128,128); Gray, RGB=(128,128,128); AppWorkspace, RGB=(128,128,128)
            '   Navy, RGB=(0,0,128); Navy, RGB=(0,0,128); HotTrack, RGB=(0,0,128)
            '   White, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   ButtonFace, RGB=(236,233,216); AntiqueWhite, RGB=(250,235,215); Control, RGB=(236,233,216)
            '   ButtonHighlight, RGB=(255,255,255); Transparent, RGB=(255,255,255); ActiveCaptionText, RGB=(255,255,255)
            '   ButtonShadow, RGB=(172,168,153); DarkGray, RGB=(169,169,169); ControlDark, RGB=(172,168,153)
            '   GradientActiveCaption, RGB=(61,149,255); DodgerBlue, RGB=(30,144,255); GradientActiveCaption, RGB=(61,149,255)
            '   GradientInactiveCaption, RGB=(157,185,235); LightSteelBlue, RGB=(176,196,222); GradientInactiveCaption, RGB=(157,185,235)
            '   MenuBar, RGB=(236,233,216); AntiqueWhite, RGB=(250,235,215); Control, RGB=(236,233,216)
            '   MenuHighlight, RGB=(49,106,197); RoyalBlue, RGB=(65,105,225); Highlight, RGB=(49,106,197)
            '
            Debug.WriteLine(System.Windows.Forms.VisualStyles.VisualStyleInformation.DisplayName)
            For Each sKnownColorName As String In [Enum].GetNames(GetType(KnownColor))
                Dim oBaseColor As New ColorName
                oBaseColor.Name = sKnownColorName
                oBaseColor.Color = Color.FromName(sKnownColorName)
                Dim oTestColor As Color = Color.FromArgb(255, oBaseColor.Color.R, oBaseColor.Color.G, oBaseColor.Color.B)
                Dim oNearestNamed As ColorName = GetNearestNameInternal(oTestColor)
                Dim oNearestKnown As ColorName = GetNearestKnownColorInternal(oTestColor)
                'results will vary due to the current display theme properties
                If oNearestNamed.Name <> oNearestKnown.Name Then
                    Debug.Write("'   ")
                    Debug.Write(oBaseColor.Name)
                    Debug.Write(", ")
                    Debug.Write(oBaseColor.ToRGBString)
                    Debug.Write("; ")
                    Debug.Write(oNearestNamed.Name)
                    Debug.Write(", ")
                    Debug.Write(oNearestNamed.ToRGBString)
                    Debug.Write("; ")
                    Debug.Write(oNearestKnown.Name)
                    Debug.Write(", ")
                    Debug.Write(oNearestKnown.ToRGBString)
                    Debug.WriteLine("")
                End If
            Next
        End Sub
        ''' <summary>
        ''' Dump all the Is... Properties 
        ''' <example>
        ''' Current ActiveBorder is (255, 212, 208, 200)
        ''' Color.FromArgb(255, 212, 208, 200) 'ActiveBorder
        ''' Color.FromName("Yellow")           '255, 255, 0
        ''' Color.FromArgb(255, 255, 255, 0)   'Yellow
        ''' </example>
        ''' </summary>
        <Extension()> _
        <Conditional("DEBUG")> _
        Friend Sub BreakOnIsProperties(ByVal color As Color)
            Dim I As Color = color.FromArgb(color.A, color.R, color.G, color.B)
            If I.IsEmpty Then
                Stop
            End If
            If I.IsKnownColor Then
                Stop
            End If
            If I.IsNamedColor Then
                Stop
            End If
            If I.IsSystemColor Then
                Stop
            End If
        End Sub
#End Region
    End Module
End Namespace