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Group VIII Coordination Chemistry of a Pincer-Type Bis(8-quinolinyl)amido Ligand

Betley, Theodore A. and Qian, Baixin A. and Peters, Jonas C. (2008) Group VIII Coordination Chemistry of a Pincer-Type Bis(8-quinolinyl)amido Ligand. Inorganic Chemistry, 47 (24). pp. 11570-11582. ISSN 0020-1669. doi:10.1021/ic801047s.

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This paper provides an entry point to the coordination chemistry of the group VIII chemistry of the bis(8-quinolinyl)amine (BQA) ligand. In this context, mono- and disubstituted BQA complexes of iron, ruthenium, and osmium are described. For example, the low-spin bis-ligated Fe(III) complex [Fe(BQA)2][BPh4] has been prepared via amine addition to FeCl3 in the presence of a base and NaBPh4. Complexes featuring a single BQA ligand are more readily prepared for Ru and Os. Auxiliary ligands featuring a single BQA ligand, along with two other L-type donor ligands, allow for a variety of ligand types to occupy a sixth coordination site. Representative examples include the halide and pseudohalide complexes trans-(BQA)MX(PPh3)2 (M = Ru, Os; X = Cl, Br, N3, OTf), as well as the hydride and alkyl complexes trans-(BQA)RuH(PMe3)2 and trans-(BQA)RuMe(PMe3)2. Electrochemical studies are discussed that help to contextualize the BQA ligand with respect to its neutral counterpart 2,2′,2′′-terpyridine (terpy) in terms of electron-releasing character. Bidentate ligands have been explored in conjunction with the BQA ligand. Thus, the bidentate, monoanionic aryl(8-quinolinyl)amido ligand 3,5-(CF3)2-(C6H3)QA has been installed onto the (BQA)Ru platform to provide (BQA)Ru(3,5-(CF3)2-(C6H3)QA)(PPh3). A bis(phosphino)borate ligand stabilizes the five-coordinate complex [Ph2B(CH2PPh2)2]Ru(BQA). Finally, access to dinitrogen complexes of the types [(BQA)Ru(N2)(PPh3)2][PF6], [(BQA)Ru(N2)(PMe3)2][PF6], and [(BQA)Os(N2)(PPh3)2][PF6] is provided by exposure of the sixth coordination site under a N2 atmosphere.

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Peters, Jonas C.0000-0002-6610-4414
Additional Information:Copyright © 2008 American Chemical Society. Received June 11, 2008. Publication Date (Web): November 13, 2008. J.C.P. is grateful to the NSF for financial support of this work (CHE-0750234 and CHE-0132216). T.A.B. is grateful to the Department of Defense for a graduate research fellowship. Supporting Information: Crystallographic data (PDF and CIF). This material is available free of charge via the Internet at
Funding AgencyGrant Number
National Science FoundationCHE-0750234
National Science FoundationCHE-0132216
Department of DefenseUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:BETic08
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:12859
Deposited By: Archive Administrator
Deposited On:08 Jan 2009 21:45
Last Modified:08 Nov 2021 22:33

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