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

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.

SUBMITTER: Honeyman GW 

PROVIDER: S-EPMC8152701 | biostudies-literature |

REPOSITORIES: biostudies-literature