September 15, 2019, 06:11:30 AM
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Topic: Does HMPA Really Coordinate through Nitrogen?  (Read 199 times)

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Offline workingundergrad1896

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Does HMPA Really Coordinate through Nitrogen?
« on: June 09, 2019, 09:40:15 AM »
Most surface online sources (i.e. wikipedia) seem to quote HMPA as coordinating through the nitrogen atom. Fine, nitrogen is less electron negative, and thus more basic, I get that.

But in the case of HMPA, wouldn't the oxygen be a more powerful coordinator/donor, due to ionic contributions? The donating effects of all those nitrogen lone pairs, combined with the withdrawing effect of the oxygen atom, would that not effectively make the oxygen quite polarised and thus give it stronger coordinating power to a cation due to charge based interactions? I'm probably making this up but I can't actually find any references or evidence to back up either possibility (if coordinating through oxygen even is a possibility...). What I'm trying to say is that, is the oxygen not more nucleophilic and/or basic than the nitrogen, due to the inductive effects of those nitrogens and the withdrawing effect of the oxygen?

Any help much appreciated..

Offline rolnor

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Re: Does HMPA Really Coordinate through Nitrogen?
« Reply #1 on: June 09, 2019, 09:57:08 AM »
I think you have coordination from oxygen, one substitute that is used is N,N-dimethylpropyl urea (DMPU) and this molecule has the nitrogens in a stericaly hindered way and still its strongly coordinating. Edit: there is a difference, in HMPA the nitrogens are not sp2 and this can make them strongly coordinating?

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