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Issue 25, 2020
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A regioselectively 1,1′,3,3′-tetrazincated ferrocene complex displaying core and peripheral reactivity

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Abstract

Regioselective 1,1′,3,3′-tetrazincation [C–H to C–Zn(tBu)] of ferrocene has been achieved by reaction of a fourfold excess of di-t-butylzinc (tBu2Zn) with sodium 2,2,6,6-tetramethylpiperidide (NaTMP) in hexane solution manifested in the trimetallic iron–sodium–zinc complex [Na4(TMP)4Zn4(tBu)4{(C5H3)2Fe}], 1. X-ray crystallographic studies supported by DFT modelling reveal the structure to be an open inverse crown in which two [Na(TMP)Zn(tBu)Na(TMP)Zn(tBu)]2+ cationic units surround a {(C5H3)2Fe}4− tetraanion. Detailed C6D6 NMR studies have assigned the plethora of 1H and 13C chemical shifts of this complex. It exists in a major form in which capping and bridging TMP groups interchange, as well as a minor form that appears to be an intermediate in this complicated exchange phenomenon. Investigation of 1 has uncovered two distinct reactivities. Two of its peripheral t-butyl carbanions formally deprotonate toluene at the lateral methyl group to generate benzyl ligands that replace these carbanions in [Na4(TMP)4Zn4(tBu)2(CH2Ph)2{(C5H3)2Fe}], 2, which retains its tetrazincated ferrocenyl core. Benzyl-Na π-arene interactions are a notable feature of 2. In contrast, reaction with pyridine affords the crystalline product {[Na·4py][Zn(py*)2(tBu)·py]}, 3, where py is neutral pyridine (C5H5N) and py* is the anion (4-C5H4N), a rare example of pyridine deprotonated/metallated at the 4-position. This ferrocene-free complex appears to be a product of core reactivity in that the core-positioned ferrocenyl anions of 1, in company with TMP anions, have formally deprotonated the heterocycle.

Graphical abstract: A regioselectively 1,1′,3,3′-tetrazincated ferrocene complex displaying core and peripheral reactivity

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Supplementary files

Article information


Submitted
18 Mar 2020
Accepted
26 Mar 2020
First published
27 Mar 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 6510-6520
Article type
Edge Article

A regioselectively 1,1′,3,3′-tetrazincated ferrocene complex displaying core and peripheral reactivity

G. W. Honeyman, D. R. Armstrong, W. Clegg, E. Hevia, A. R. Kennedy, R. McLellan, S. A. Orr, J. A. Parkinson, D. L. Ramsay, S. D. Robertson, S. Towie and R. E. Mulvey, Chem. Sci., 2020, 11, 6510
DOI: 10.1039/D0SC01612H

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