Issue 14, 2016

Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenes

Abstract

A fluorenyl (Fl) tethered diamine was synthesised by nucleophilic substitution of (bromoethyl)fluorene with a diisopropylphenyl (Dipp) substituted diamine to give FlC2H4N(H)C2H4N(H)Dipp (1a) in good yield (85%). Lithiation of 1a with n-BuLi proceeded with coordination of the Li cation to the aromatic fluorenide ring (2), and with subsequent equivalents of n-BuLi, the secondary amines were then sequentially deprotonated. A fluorenyl-tethered N-heterocyclic stannylene (NHSn) was synthesised from the reaction of 1a with SnN′′2 {N′′ = N(SiMe3)2} as a neutral dimeric species (5), and this was deprotonated with LiN′′ to give the corresponding dianionic fluorenide-tethered NHSn (6). Reactions of [{Rh(cod)(μ-Cl)}2] with the mono-deprotonated ligand 2 led to the formation of a mixed-donor amide–amine Rh(I) compound (7), whereas reactions with the anionic NHSn 6 led to a Rh–fluorenyl complex of low stability with an uncoordinated pendent NHSn arm, which X-ray crystallography showed to be dimeric in the solid state.

Graphical abstract: Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenes

Supplementary files

Article information

Article type
Paper
Submitted
16 okt 2015
Accepted
19 dec 2015
First published
04 jan 2016
This article is Open Access
Creative Commons BY license

Dalton Trans., 2016,45, 6282-6293

Author version available

Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenes

M. Roselló-Merino and S. M. Mansell, Dalton Trans., 2016, 45, 6282 DOI: 10.1039/C5DT04060D

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