Facile Deep and Ultradeep Hydrodesulfurization by the [((i)Pr3P)Ni]5H6 Cluster Compared to Mononuclear Ni Sources

Manar M Shoshani; Samuel A Johnson

doi:10.1021/acs.inorgchem.5b02383

Facile Deep and Ultradeep Hydrodesulfurization by the [((i)Pr3P)Ni]5H6 Cluster Compared to Mononuclear Ni Sources

Inorg Chem. 2015 Dec 21;54(24):11977-85. doi: 10.1021/acs.inorgchem.5b02383. Epub 2015 Dec 3.

Authors

Manar M Shoshani¹, Samuel A Johnson¹

Affiliation

¹ Department of Chemistry and Biochemistry, University of Windsor , Sunset Avenue 401, Windsor, Ontario N9B 3P4, Canada.

PMID: 26632649
DOI: 10.1021/acs.inorgchem.5b02383

Abstract

The pentanuclear nickel cluster [((i)Pr3P)Ni]5H6 facilitates the room-temperature hydrodesulfurization of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethydibenzothiophene. These reactions provide the new tetranuclear nickel hydride sulfide [((i)Pr3P)Ni]4(μ-H)4(μ4-S) (1). In comparison, the dinuclear dinitrogen nickel complex [((i)Pr3P)2Ni]2(μ-N2) undergoes oxidative addition of the C-S bonds of dibenzothiophene and 4-methyl dibenzothiophene to provide the metallacycles Ni3(P(i)Pr3)3C12H8S (2) and Ni3(P(i)Pr3)3C13H10S (3), respectively, but 4,6-dimethydibenzothiophene is unreactive, even with heating to 70 °C for a week. The reaction of [((i)Pr3P)Ni]5H6 with SP(i)Pr3 in toluene provided [((i)Pr3P)Ni]5H6(S) (4), which was observed and characterized by NMR spectroscopy. The addition of vinyltrimethylsilane to 4 provided the best synthetic route to 1, with ((i)Pr3P)Ni(η(2)-CH2═CHSiMe3)2 (5) generated as a byproduct.

Publication types

Research Support, Non-U.S. Gov't