Toward multifunctional Mo(VI-IV) complexes: cis-dioxomolybdenum(VI) complexes containing hydrogen-bond acceptors or donors

Inorganic Chemistry
Lyndal M R HillCharles G Young

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 nu(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 A and angle(MoO2)av=103.2 degrees. 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 degrees (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) degrees, respectively (conformation 2). Conformations 1 and 2 are both ob...Continue Reading

References

May 25, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·R R Conry, A A Tipton
Mar 28, 1996·Chemical Reviews·Neil G. Connelly, William E. Geiger
Nov 7, 1996·Chemical Reviews·Russ Hille
Jan 5, 2006·Journal of the American Chemical Society·Christian J DoonanCharles G Young
Feb 28, 2006·Inorganic Chemistry·Michael S MalarekCharles G Young

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Citations

Jul 3, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Rafał Petrus, Piotr Sobota
Feb 23, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexandros A KitosVassilios Nastopoulos
Sep 17, 2010·Inorganic Chemistry·Victor W L NgCharles G Young

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