Campbell, R., Kennedy, A. R., McLellan, R., Robertson, S. D., Sproules, S. and Mulvey, R. E. (2017) Contrasting the group 6 metal-metal bonding in sodium dichromate(II) and sodium dimolybdate(II) polymethyl complexes: synthetic, X-ray crystallographic and theoretical studies. Dalton Transactions, 46(17), pp. 5650-5659. (doi: 10.1039/C6DT04644D) (PMID:28145549)
|
Text
136716.pdf - Accepted Version 1MB |
Abstract
Extending the class of group 6 metal–metal bonded methylate compounds supported by alkali metal counter-ions, the first sodium octamethylmolybdate(II) complex [(TMEDA)Na]4Mo2Me8 and heptamethylchromate(II) relations [(donor)Na]3Cr2Me7 (donor is TMEDA or TMCDA) are reported. The former was made by treating [(Et2O)Li]4Mo2Me8 with four equivalents of NaOtBu/TMEDA in ether; whereas the latter resulted from introducing TMEDA or TMCDA to ether solutions of octamethyldichromate [(Et2O)Na]4Cr2Me8. X-ray crystallography revealed [(TMEDA)Na]4Mo2Me8 is dimeric with square pyramidal Mo centres [including a short Mo–Mo interaction of 2.1403(3) Å] each with four methyl groups in a mutually eclipsed conformation. In dinuclear [(TMCDA)Na]3Cr2Me7 trigonal bi-pyramidal Cr centres each bond to three terminal methyl groups and one common Me bridge, that produces a strikingly short Cr–Cr contact of 1.9136(4) Å. Broken symmetry density functional theoretical calculations expose the multiconfigurational metal–metal bonding in these compounds with a Mo–Mo bond order of 3 computed for octamethylmolybdate(II). This is contrasted by the single Cr–Cr bond in heptamethylchromate(II) where the singlet ground state is derived by strong antiferromagnetic coupling between adjacent metal ions.
Item Type: | Articles |
---|---|
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Sproules, Dr Stephen |
Authors: | Campbell, R., Kennedy, A. R., McLellan, R., Robertson, S. D., Sproules, S., and Mulvey, R. E. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Dalton Transactions |
Publisher: | Royal Society of Chemistry |
ISSN: | 1477-9226 |
ISSN (Online): | 1477-9234 |
Published Online: | 26 January 2017 |
Copyright Holders: | Copyright © 2017 The Royal Society of Chemistry |
First Published: | First published in Dalton Transactions 46(17): 5650-5659 |
Publisher Policy: | Reproduced in accordance with the copyright policy of the publisher |
University Staff: Request a correction | Enlighten Editors: Update this record