You are pretty close, but since <emailTo> is an element (not an attribute), you need to use:
select T.id, T.xml_data.value('(SSRSReport/email/emailTo)[1]', 'varchar(50)') as PropertyName
Use /emailTo (not /@emailTo ) as the last part of an XPath expression.
In addition, the .exist() function can check for the presence of an XML element (or attribute), so you can check if the <emailTo> element <emailTo> (or does not exist), but you cannot compare with the value. So your WHERE invalid - you probably wanted:
where T.xml_data.value('(SSRSReport/email/emailTo)[1]', 'varchar(50)') = 'xyz.com'
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