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

Drover, Marcus W. and Peters, Jonas C. (2018) Expanding the allyl analogy: accessing η³-P,B,P diphosphinoborane complexes of group 10. Dalton Transactions, 47 (11). pp. 3733-3738. ISSN 1477-9226. PMCID PMC6005356. doi:10.1039/c8dt00058a.

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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.

Item Type:Article
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URLURL TypeDescription Information CentralArticle
Drover, Marcus W.0000-0002-2186-1040
Peters, Jonas C.0000-0002-6610-4414
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.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:11
PubMed Central ID:PMC6005356
Record Number:CaltechAUTHORS:20180215-085923720
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84844
Deposited By: Tony Diaz
Deposited On:15 Feb 2018 23:04
Last Modified:15 Mar 2022 20:45

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