Ligand Assisted Volatilization and Thermal Stability of [(t-BuN=)2MoCl2]2

09 August 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Volatile molybdenum containing compounds have successfully been utilized for the atomic layer deposition of MoNx, MoO3, MoS2, and MoCxNy. Most of the reported volatile molybdenum containing compounds have been prepared via salt metathesis reactions of bis(tert-butylimido)-dichloromolybdenum(VI), with anionic nitrogen based ligands. Herein we describe the preparation of several adducts of [(t-BuN=)2MoCl2]2 (2) via ligand exchange reactions with various neutral ligands, including both mono- and bidentate ethers, amines, and phosphines, as well as an N-heterocyclic carbene (NHC). These compounds have been characterized using NMR spectroscopy, elemental analysis, and the solid-state structures have been determined using single crystal X-ray crystallography. The volatility and thermal stability of all compounds have been assessed using TGA and DSC, showing that the coordinated ligands can improve the volatility, but in many cases the gas phase species reverts to 2. This highlights a strategy for using coordinative ligands that are easily thermolyzed during evaporation and delivery yet improve the volatility of a key precursor.


X-ray crystallography
atomic layer deposition
thermogravimetric analysis
Differential Scanning Calorimetry
thermal stability
Vapor deposition precursors

Supplementary materials

MoLigand SI


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.