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Issue 46, 2016
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N–H cleavage as a route to new pincer complexes of high-valent rhenium

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Abstract

A novel PNN-type pincer ligand has been accessed via imine reduction with LiAlH4 to provide the phosphine diamino proligand, PNHNH (1). The ligand, 1, as well as PNHP can be metallated directly, via N–H cleavage, with L2ReOX2(OEt) precursors to access six-coordinate (PNP)ReOCl2 (2) and (PNNH)ReOX2 (3-Cl, X = Cl; 3-Br, X = Br) in good yield. 3-Cl and 3-Br undergo dehydrohalogenation upon treatment with NEt3, furnishing the five-coordinate phosphine/diamido PNN-type compounds (PNN)ReOX (4-Cl, X = Cl; 4-Br, X = Br) in excellent yield, presenting as a mixture of rotameric diasteromers. The reversibility of this deprotonation, and the coordinative unsaturation of 4-Cl is shown in reactions with HCl(aq) and PMe3 providing 3-Cl and 4-PMe3, respectively. Treatment of 4-Cl with AgOAc, AgOTf, or NaHBEt3 lead to formation of (PNN)ReO(OAc) (4-OAc), (PNN)ReO(OTf) (4-OTf), and (PNN)ReO(H) (4-H), all isolated in excellent yields in varying diasteromeric ratios. The nature of the isomerism was analyzed based on solid-state structural studies and solution NMR data.

Graphical abstract: N–H cleavage as a route to new pincer complexes of high-valent rhenium

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Publication details

The article was received on 19 Sep 2016, accepted on 14 Oct 2016 and first published on 17 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT03640F
Citation: Dalton Trans., 2016,45, 18532-18540
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    N–H cleavage as a route to new pincer complexes of high-valent rhenium

    A. J. Kosanovich, W. Shih, R. Ramírez-Contreras and Oleg. V. Ozerov, Dalton Trans., 2016, 45, 18532
    DOI: 10.1039/C6DT03640F

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