Construction of heterometallic clusters in a small peptide scaffold as [NiFe]-hydrogenase models: Development of a synthetic methodology

Arnab Dutta, G. Alexander Hamilton, Hilairy Hartnett, Anne Jones

Research output: Contribution to journalArticle

16 Scopus citations

Abstract

[NiFe]-hydrogenases are enzymes that catalyze the reversible interconversion of protons and hydrogen at a heterobimetallic site containing Ni and Fe. This organometallic site has served as an inspiration for the synthesis of a number of biomimetic complexes, but, unfortunately, most close structural mimics have shown little to no reactivity with either of the substrates for hydrogenases. This suggests that interactions between the metallo-active site and the protein scaffold are crucial in tuning reactivity. As a first step toward development of peptide-based models, in this paper we demonstrate a synthetic strategy for construction of peptide coordinated, cysteinyl thiolate bridged Ni-M complexes in which M is a hetero-organometallic fragment. We utilize the seven amino acid peptide ACDLPCG as a scaffold for construction of these peptide-coordinated metallocenters. This peptide binds Ni in an N 2S2 environment consisting of the amino terminus, an amide nitrogen, and the two cysteinyl thiolates. We show that these thiolates serve as reactive sites for formation of heterometallic complexes in which they serve as bridging ligands. The method is general, and a number of heterometallic fragments including Ru(η6-arene)2+, M(CO) 4(piperidine) for M = Mo and W, and Fe2(CO)6 were successfully incorporated, and the resulting metallopeptides characterized via a range of spectroscopic techniques. This methodology serves as the first step to construction of hydrogenase peptidomimetics that incorporate defined outer coordination sphere interactions intended to tune reactivity.

Original languageEnglish (US)
Pages (from-to)9580-9588
Number of pages9
JournalInorganic chemistry
Volume51
Issue number18
DOIs
StatePublished - Sep 17 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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