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Published March 21, 2018 | Supplemental Material + Accepted Version
Journal Article Open

Expanding the allyl analogy: accessing η³-P,B,P diphosphinoborane complexes of group 10

Abstract

Using the diphosphinoborane, (PPh₂)₂BMes (Mes = 2,4,6-Me₃₆6H₃), we report the first examples of η³-P,B,P-ligated complexes using Ni(0) and Pt(II). Reaction of (PPh₂)₂BMes with Ni(COD)₂ or Pt(COD)Me₂ (COD = 1,5-cyclooctadiene) results in gradual COD displacement to give [η³-P,B,P-(PPh₂)₂BMes]Ni(COD) (3) or [η³-P,B,P-(PPh₂)₂BMes]Pt(CH₃)₂ (6). Complex 3 serves as a versatile Ni-containing synthon for the preparation of square planar or tetrahedral Ni(0) complexes. Notably, the M–B interaction in these systems is non-negligible – with coordination resulting in an upfield shift of ca. 80 ppm in the ¹¹B NMR spectrum. We also show that treatment of the Pt^(IV) halide precursor, [PtMe₃I]₄ with this ligand framework results in migration of X-type ligands (CH₃− and I−) to boron and reductive elimination of ethane (C₂H₆) to give a distorted square planar zwitterionic Pt^(II) complex, Pt[κ^2-P,P-(PPh₂)₂B(Mes)(CH₃)][κ²-P,P-(PPh₂)₂B(Mes)(I)] (10). This reactivity suggests the feasibility of (PPh₂)₂BMes-ligand-induced labilization of M–X ligands.

Additional Information

© 2018 The Royal Society of Chemistry. Received 6th January 2018, Accepted 2nd February 2018. First published on 5th February 2018. This work was supported by the NIH (GM070757), NSERC (Banting PDF award to MWD), and the Resnick Sustainability Institute at Caltech (Postdoctoral award to MWD). We thank Larry Henling and Mike Takase for assistance with X-ray crystallography. There are no conflicts to declare.

Attached Files

Accepted Version - nihms-974447.pdf

Supplemental Material - c8dt00058a1_si.pdf

Supplemental Material - c8dt00058a2.cif

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Created:
August 19, 2023
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October 18, 2023