bis(pinacolato)diborone

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CAS: 10221-56-4
MF: C12H24B2O5
MW: 269.93796
Synonyms: bis(pinacolato)diborone

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Nilay Hazari

Yale University
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Co-reporter: Hee-Won Suh, Louise M. Guard, Nilay Hazari
pp: 37-43
Publication Date(Web):14 December 2014
DOI: 10.1016/j.poly.2014.05.078
Tridentate PSiP pincer ligands featuring two phosphine donors and an anionic Si donor have attracted considerable attention in recent years. Here, we report the synthesis of the η3-cyclooctenyl complex, (PhPSiP)Ni(η3-cyclooctenyl) (1; PhPSiP = Si(Me)(2-PPh2–C6H4)2) through the reaction of Ni(COD)2 with PhPSiHP (PhPSiHP = HSi(Me)(2-PPh2–C6H4)2). We propose, that as a result of β-hydride elimination of 1,3-COD, 1 can act as a synthetic equivalent for (PhPSiP)NiH. The reaction of 1 with a variety of different reagents including another equivalent of PhPSiHP to form (PhPSiP)2Ni (2), 1,3-COD and H2, PPh3 to form the Ni(0) species (PhPSiHP)Ni(PPh3) (3) and 1,3-COD and 2,6-lutidine·HCl to generate (PhPSiP)NiCl (4), 1,3-COD and H2 are in agreement with this hypothesis. In addition, in the reaction of 1 with BH3·THF, (PhPSiP)Ni(κ2-BH4) (5) was observed but could not be isolated. This reaction presumably proceeds via (PhPSiP)NiH. This is supported by the observation that the reaction of (CyPSiP)NiH (CyPSiP = Si(Me)(2-PCy2-C6H4)2) with BH3·THF formed (CyPSiP)Ni(κ2-BH4) (6). Catalytic reactions such as alkene isomerization and CO2 reduction using 1 as precatalyst are also consistent with a nickel hydride being accessible. Compounds 1, 2 and 6 were characterized by X-ray crystallography.The synthesis and reactivity of the η3-cyclooctenyl complex, (PhPSiP)Ni(η3-cyclooctenyl)(PhPSiP = Si(Me)(2-PPh2–C6H4)2), which can act as a mask for a Ni hydride, is reported.Image for unlabelled figure

Adam J. Matzger

The University of Michigan
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Melanie S. Sanford

University of Michigan
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Nathaniel K. Szymczak

University of Michigan
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Oleg V. Ozerov

Texas A&M University
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Ryan J. Trovitch

Arizona State University
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Jun Okuda

RWTH Aachen University
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HIROSHI NAKAZAWA

Osaka City University
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MASUMI ITAZAKI

Osaka City University
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Michael S. Hill

University of Bath
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