(dme)MCl_3(NNPh_2) (dme= dimethoxyethane; M= Nb, Ta): A Versatile Synthon for [Ta═NNPh_2] Hydrazido(2-) Complexes
- Creators
- Tonks, Ian A.
- Bercaw, John E.
Abstract
Complexes (dme)TaCl_3(NNPh_2) (1) and (dme)NbCl_3(NNPh_2) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl5 and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV−vis, ^(1)H NMR, and ^(13)C NMR spectroscopy and contains a κ^(1)-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an N_(α)−N_(β) antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the κ^(1)-bound [Ta−NNPh_2] moiety.
Additional Information
© 2010 American Chemical Society. Published In Issue: May 17, 2010; Article ASAP: April 19, 2010; Received: March 02, 2010. We thank Dr. Nilay Hazari (Yale) for assistance with the DFT calculations. DFT calculations were carried out using the Molecular Graphics and Computation Facility, College of Chemistry, University of California, Berkeley, CA, with equipment support from NSF Grant CHE- 0233882. We acknowledge Dr. Jay Labinger and Professor Harry Gray (Caltech) and Professor Lisa McElwee-White (University of Florida) for fruitful discussions. We also thank Lawrence Henling and Dr. Michael Day for assistance with the X-ray studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094. This work has been supported by USDOE Office of Basic Energy Sciences (Grant DE-FG03-85ER13431).Attached Files
Supplemental Material - ic1004193_si_001.pdf
Supplemental Material - ic1004193_si_002.cif
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Additional details
- Eprint ID
- 18561
- Resolver ID
- CaltechAUTHORS:20100604-110437467
- NSF
- CHE-0233882
- NSF
- CHE-0639094
- U. S. Department of Energy
- DE-FG03-85ER13431
- Created
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2010-06-07Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field