Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/8139
Title: Toward Multifunctional Mo(VI−IV) Complexes: cis-Dioxomolybdenum(VI) Complexes Containing Hydrogen-Bond Acceptors or Donors
Contributor(s): Hill, LMR (author); Taylor, Michelle K  (author); Ng, VWL (author); Young, CG (author)
Publication Date: 2008
DOI: 10.1021/ic701957b
Handle Link: https://hdl.handle.net/1959.11/8139
Abstract: The complexes cis-TpiPrMoVIO2(OAr-R) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate, -OAr-R = hydrogen-bonding phenolate derivative) are formed upon reaction of TpiPrMoO2Cl, HOAr-R, and NEt3 in dichloromethane. The orange, diamagnetic, dioxo−Mo(VI) complexes exhibit strong ν(MoO2) IR bands at ca. 935 and 900 cm-1 and NMR spectra indicative of Cs symmetry. They undergo electrochemically reversible, one-electron reductions at potentials in the range −0.836 to −0.598 V vs SCE; the only exception is the 2-CO2Ph derivative, which exhibits an irreversible reduction at −0.924 V. The complexes display distorted octahedral geometries, with a cis arrangement of terminal oxo ligands and with d(Mo=O)av = 1.695 Å and (MoO2)av = 103.2°. The R groups of the 2-CHO and 2-NHCOMe derivatives are directed away from the oxo groups and into a cleft in the TpiPr ligand; these derivatives are characterized by Mo−O−Cipso angles of ca. 131° (conformation 1). The R group(s) in the 2-CO2Me and 2,3-(OMe)2 derivatives lie above the face of the three O-donor atoms (directed away from the TpiPr ligand) and the complexes display Mo−O−Cipso angles of 153.1(2) and 149.7(2)°, respectively (conformation 2). Conformations 1 and 2 are both observed in the positionally disordered 2-COMe and 2-COEt derivatives, the two conformers having Mo−O−Cipso angles of 130−140 and >150°, respectively. The 3-COMe and 3-NEt2 derivatives have substituents that project away from the TpiPr ligand and Mo−O−Cipso angles of 134.2(2) and 147.7(2)°, respectively. Many of the complexes exhibit fluxional behavior on the NMR time scale, consistent with the rapid interconversion of two conformers in solution.
Publication Type: Journal Article
Source of Publication: Inorganic Chemistry, 47(3), p. 1044-1052
Publisher: American Chemical Society
Place of Publication: United States of America
ISSN: 1520-510X
0020-1669
Field of Research (FOR): 030207 Transition Metal Chemistry
030201 Bioinorganic Chemistry
Socio-Economic Outcome Codes: 970103 Expanding Knowledge in the Chemical Sciences
Peer Reviewed: Yes
HERDC Category Description: C1 Refereed Article in a Scholarly Journal
Statistics to Oct 2018: Visitors: 207
Views: 284
Downloads: 0
Appears in Collections:Journal Article

Files in This Item:
2 files
File Description SizeFormat 
Show full item record

SCOPUSTM   
Citations

19
checked on Nov 26, 2018

Page view(s)

38
checked on Jan 11, 2019
Google Media

Google ScholarTM

Check

Altmetric


Items in Research UNE are protected by copyright, with all rights reserved, unless otherwise indicated.