CaltechAUTHORS
  A Caltech Library Service

Groups 5 and 6 Terminal Hydrazido(2−) Complexes: N_β Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States

Tonks, Ian A. and Durrell, Alec C. and Gray, Harry B. and Bercaw, John E. (2012) Groups 5 and 6 Terminal Hydrazido(2−) Complexes: N_β Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States. Journal of the American Chemical Society, 134 (17). pp. 7301-7304. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20120530-084227048

[img]
Preview
PDF - Supplemental Material
See Usage Policy.

173Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

202Kb

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20120530-084227048

Abstract

Brightly colored terminal hydrazido(2−) (dme)MCl_3(NNR_2) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl_4(NNR_2) complexes have been synthesized and characterized. Perturbing the electronic environment of the β (NR_2) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the N_β lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize N_β in order to reduce the overlap between the Nb═Nα π bond and the Nβ lone pair. For W complexes, increasing the energy of N_β eventually leads to reduction from formally [W^(VI)≡N–NR_2] with a hydrazido(2−) ligand to [W^(IV)═N═NR_2] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja302275jDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja302275jPublisherArticle
Additional Information:© 2012 American Chemical Society. Received: March 7, 2012. Publication Date (Web): April 16, 2012. We 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 (CHE-0639094) to the California Institute of Technology. This work was supported by the U.S. DOE Office of Basic Energy Sciences (DE-FG03-85ER13431 to J.E.B.). Photophysics investigations were supported by an NSF Center for Chemical Innovation Grant (CHE-0802907 to H.B.G.).
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSF CRIF:MU AwardCHE-0639094
Department of Energy (DOE) Office of Basic Energy Sciences DE-FG03-85ER13431
NSF Center for Chemical InnovationCHE-0802907
Record Number:CaltechAUTHORS:20120530-084227048
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120530-084227048
Official Citation:Groups 5 and 6 Terminal Hydrazido(2−) Complexes: Nβ Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States Ian A. Tonks, Alec C. Durrell, Harry B. Gray, and John E. Bercaw Journal of the American Chemical Society 2012 134 (17), 7301-7304
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:31693
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:30 May 2012 15:58
Last Modified:04 Apr 2014 01:48

Repository Staff Only: item control page