Yes, rgba(hex, opacity) is not allowed in CSS (but it is possible in SCSS), it has to be rgba(red, green, blue, opacity). You want something like:
:style="{ 'background-color': `rgba(${ item.red }, ${ item.green }, ${ item.blue }, 0.5)` }"
See also conversion between RGB and hex.
Edit: Since you are doing this in a bound attribute, you can define a helper function to convert your hex_code to RGB suitable for CSS:
:style="{ 'background-color': `rgba(${hexCodeToCSSRGB(item.hex_code)}, 0.5)` }"
With this helper function (adapted from the linked answer):
function hexToRgb(hex) {
  var result = /^#?([a-f\d]{2})([a-f\d]{2})([a-f\d]{2})$/i.exec(hex);
  return result
    ? `${parseInt(result[1], 16)}, ${parseInt(result[2], 16)}, ${parseInt(result[3], 16)}`
    : "0, 0, 0";
}
Note that this will convert "#ff00aa" to "255, 0, 170", so in your background-color, you would end up with rgba(255, 0, 170, 0.5).