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Pincer-like Amido Complexes of Platinum, Palladium, and Nickel

Peters, Jonas C. and Harkins, Seth B. and Brown, Steven D. and Day, Michael W. (2001) Pincer-like Amido Complexes of Platinum, Palladium, and Nickel. Inorganic Chemistry, 40 (20). pp. 5083-5091. ISSN 0020-1669.

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The ligands bis(8-quinolinyl)amine (BQAH, 1), (2-pyridin-2-yl-ethyl)-(8-quinolinyl)amine (2-pyridin-2-yl-ethyl-QAH, 2), o-dimethylaminophenyl(8-quinolinyl)amine (o-(NMe_2)Ph-QAH, 3), and 3,5-dimethylphenyl(8-quinolinyl)amine (3,5-Me_2Ph-QAH, 4) have been prepared in high yield from aryl halide and amine precursors by palladium-catalyzed coupling reactions. Deprotonation of 1 with ^nBuLi in toluene affords the lithium amide complex [Li][BQA] (5), whose dimeric solid-state crystal structure is presented. Lithium amide 5 was transmetalated by TlOTf to afford the thallium(I) amido complex [Tl][BQA] (6). An X-ray structural study of 6 shows it to be a 1:1 complex of the BQA ligand and Tl. Entry into the group 10 chemistry of the parent ligand 1 was effected by both protolytic and metathetical strategies. Thus, the divalent chloride complexes (BQA)PtCl (7), (BQA)PdCl (8), and (BQA)NiCl (9) were prepared and fully characterized. An X-ray structural study for each of these three complexes shows them to be well-defined, square-planar complexes in which the auxiliary BQA ligand binds in a planar, ^η3-fashion. For comparison, the reactivity of ligands 2−4 with (COD)PtCl_2 was studied. While reaction with ligand 2 afforded an ill-defined product mixture, ligands 3 and 4 reacted with (COD)PtCl_2 to generate the unusual alkyl complexes (o-(NMe_2)Ph-QA)Pt(1,2-η^2-6-σ-cycloocta-1,4-dienyl) (10) and (3,5-Me_2Ph-QA)Pt(1,2-η^2-6-σ-cycloocta-1,4-dienyl) (11), both of which have been structurally characterized.

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Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2001 American Chemical Society. Publication Date (Web): August 24, 2001. Received March 27, 2001. We wish to thank the California Institute of Technology and the Dreyfus Foundation for their generous support of this research through a start-up grant and a Dreyfus Foundation New Faculty Award.
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Dreyfus Foundation UNSPECIFIED
Dreyfus Foundation New Faculty Award UNSPECIFIED
Issue or Number:20
Record Number:CaltechAUTHORS:20140731-091158681
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Official Citation: Pincer-like Amido Complexes of Platinum, Palladium, and Nickel Jonas C. Peters,*, Seth B. Harkins,Steven D. Brown, and, and Michael W. Day Inorganic Chemistry 2001 40 (20), 5083-5091
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47697
Deposited By: Ruth Sustaita
Deposited On:31 Jul 2014 16:53
Last Modified:26 Nov 2019 11:15

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