Rails has a lot of conventions (aka 'magic') that obscures the underlying language, so it is generally not a great way of learning ruby. At least that is my experience.
I am a volunteer mentor at Mendicant University (a free online school for intermediate ruby developers, started by Gregory Brown). Many students come to ruby through rails, and we find that they often have a lot of un-learning to do, to get back to basic design principles and how to apply these in ruby.
I highly recommend taking the MU core course when it is offered again in January (look for an announcement probably next month). Many students apply who are new to ruby but experienced in other languages, so it would be a good fit for you. I also recommend Greg's book Ruby Best Practices, and ongoing Practicing Ruby series.
Eric