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Expanding the allyl analogy: accessing η^3-P,B,P diphosphinoborane complexes of group 10

Drover, Marcus W. and Peters, Jonas C. (2018) Expanding the allyl analogy: accessing η^3-P,B,P diphosphinoborane complexes of group 10. Dalton Transactions, 47 (11). pp. 3733-3738. ISSN 1477-9226. http://resolver.caltech.edu/CaltechAUTHORS:20180215-085923720

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Abstract

Using the diphosphinoborane, (PPh_2)_2BMes (Mes = 2,4,6-Me_3C_6H_3), we report the first examples of η^3-P,B,P-ligated complexes using Ni(0) and Pt(II). Reaction of (PPh_2)_2BMes with Ni(COD)_2 or Pt(COD)Me_2 (COD = 1,5-cyclooctadiene) results in gradual COD displacement to give [η^3-P,B,P-(PPh_2)_2BMes]Ni(COD) (3) or [η^3-P,B,P-(PPh_2)_2BMes]Pt(CH_3)_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 ^(11)B NMR spectrum. We also show that treatment of the Pt^(IV) halide precursor, [PtMe_3I]_4 with this ligand framework results in migration of X-type ligands (CH_3− and I−) to boron and reductive elimination of ethane (C_2H_6) to give a distorted square planar zwitterionic Pt^(II) complex, Pt[κ^2-P,P-(PPh_2)_2B(Mes)(CH_3)][κ^2-P,P-(PPh_2)_2B(Mes)(I)] (10). This reactivity suggests the feasibility of (PPh_2)_2BMes-ligand-induced labilization of M–X ligands.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/c8dt00058aDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2018/DT/C8DT00058APublisherArticle
http://www.rsc.org/suppdata/c8/dt/c8dt00058a/c8dt00058a1.pdfPublisherSupplementary Information
ORCID:
AuthorORCID
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
Funders:
Funding AgencyGrant Number
NIHGM070757
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Record Number:CaltechAUTHORS:20180215-085923720
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180215-085923720
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84844
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:15 Feb 2018 23:04
Last Modified:13 Mar 2018 17:37

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