Cut-and-Pasting Ligands: The Structure/Function Relationships of a Thermally Robust Mo(VI) Precursor

18 August 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The bis(tert-butylimido)-molybdenum(VI) framework has previously been used for the successful atomic layer deposition and chemical vapor deposition of many molybdenum-containing thin films. We have now prepared and fully characterized a new thermally robust bis(tert-butylimido)molybdenum(VI) complex, bis(tert-butylimido)-bis(N-2-(tertbutyliminomethyl)pyrrolato)-molybdenum(VI), (tBuN)2Mo(PyrIm)2 (1), that incorporates two N,N’-κ2-monoanionic ligands. The volatility and thermal stability of 1 was measured using thermogravimetric analysis and differential scanning calorimetry, where it was found to achieve a 1 Torr of vapor pressure at 212 ºC and had an onset of thermal decomposition at 273 ºC. Comparison of its thermal properties to the known ALD precursor (tBuN)2Mo(dpamd)2 (dpamd = N,N’-diisopropyl-acetamidinato) showed that 1 exhibits a similar volatility, but with a 78 ºC improvement in thermal stability. Since 1 exhibits an excellent thermal range (61 ºC), it should be further explored for use as a vapor deposition precursor.


Precursor Design
Thermal Stability
Chemical Structure
Vapor Deposition

Supplementary materials

Supporting Information
NMR, IR and HRMS spectra; TGA plots; DSC curves; additional crystallographic information and images.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.