Wednesday, April 10, 2019

"Mechanistic studies support the formation of CH3+ as a key intermediate."

Credit: Oddity Central
Click here for Dan Singleton, critiquing a recent Science paper within an inch of its life for proposing
a methyl cation as a part of its mechanistic pathway.

I have to admit, I'm pretty sure I read the C&EN summary of the paper, and I did not notice the methyl cation. If you like physical organic chemistry, you'll enjoy Professor Singleton's thread.


13 comments:

  1. Wow... I think the only question is whether this is more embarrassing for Science than the arsenic in DNA paper.

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  2. Is it fair to say that Dr. Singleton has been possessed with the spirit of HC Brown? Recall if HC Brown ended up being right?

    Why get so bent out of shape about this kind of stuff? Singleton is trouncing on someones garden...

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    Replies
    1. "Why get so bent out of shape about this kind of stuff? Singleton is trouncing on someones garden..."

      Science is **everyone's** garden. If it's not open for debate and analysis, ** it's ** *** not *** **** science *****.
      Statements like the one you make lead to bullshit and lies..

      Delete
    2. Well, being an astute study of mechanism, Singleton certainly has the experience and insight probable theories than most. However, the proposal of methyl carbocation being an intermediate should lead ANY sophomore organic student to shake their head in disgrace at Science, the authors, the referees, and you Anon 10:30.

      Delete
    3. "Bent out of shape" was my euphemism for, IMO, Singletons shrill and abrasive style. Debate in science is always good.

      Delete
    4. Singleton mentions "dog r*pe" in this thread; presenting obscene ideas is not helping his argument. I think this could speak to his character, anon 2:15 pm

      Delete
    5. This subthread discussion of Professor Singleton's argument style has reached the end of its productive life.

      Delete
  3. Gargh, right in the "org.chem-hood"...

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  4. People are not familiar with Olah's work on superacid chemistry.

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    Replies
    1. Yeah, they didn't even need to propose a mechanism. This was figured out long ago, and highlighted by Andrei Yudin in the comments.

      https://twitter.com/andrei_yudin/status/1115247693994045442

      Delete
  5. People who accuse Singleton of overreacting to a methyl cation in the mechanism are actually missing the point. The truly egregious error happens in the next step-- CH3+ attacking SO3 on the SULFUR atom. Even when I was in high school chemistry I knew that sulfur was less electronegative than oxygen and was going to have a partial positive charge. And the resulting intermediate species with a positive charge and incomplete octet on an oxygen atom is absolutely horrendous.

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  6. I definitely have impostor syndrome when it comes to mechanisms and I shudder to think what Prof. Singleton could have done to me in a thesis defense.

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    ReplyDelete