Synthesis and vibrational spectroscopy of 57Fe-labeled models of [NiFe] hydrogenase: first direct observation of a nickel–iron interaction† †Electronic supplementary information (ESI) available: Experimental procedures, spectral data, computational chemistry details, animated vibrational modes as GIFs. See DOI: 10.1039/c4cc04572f Click here for additional data file. Click here for additional data file.

نویسندگان

  • David Schilter
  • Vladimir Pelmenschikov
  • Hongxin Wang
  • Florian Meier
  • Leland B. Gee
  • Yoshitaka Yoda
  • Martin Kaupp
  • Thomas B. Rauchfuss
  • Stephen P. Cramer
چکیده

A new route to iron carbonyls has enabled synthesis of (57)Fe-labeled [NiFe] hydrogenase mimic (OC)3(57)Fe(pdt)Ni(dppe). Its study by nuclear resonance vibrational spectroscopy revealed Ni-(57)Fe vibrations, as confirmed by calculations. The modes are absent for [(OC)3(57)Fe(pdt)Ni(dppe)](+), which lacks Ni-(57)Fe bonding, underscoring the utility of the analyses in identifying metal-metal interactions.

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Persistent four-coordinate iron-centered radical stabilized by π-donation† †Electronic supplementary information (ESI) available: Experimental, crystallographic, computational details, and crystal data for 2, 4, 5 and 8. CCDC 1057111–1057113 and 1425703. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02601f Click here for additional data file. Click here for additional data file.

Institute for Materials Chemistry and Kasugakoen, Kasuga, Fukuoka 816-8580, Ja Department of Chemistry, Graduate Schoo Sendai 980-8578, Japan Institute for Materials Chemistry and En Fukuoka 819-0395, Japan CREST, Japan Science and Technology Fukuoka 816-8580, Japan † Electronic supplementary informati crystallographic, computational details, a 1057111–1057113 and 1425703. For ESI other electro...

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Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O2-tolerant NAD+-reducing [NiFe] hydrogenase† †Electronic supplementary information (ESI) available: Representations of data analyses (Fig. S1 and S2). See DOI: 10.1039/c4sc02982h Click here for additional data file.

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of li...

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عنوان ژورنال:

دوره 50  شماره 

صفحات  -

تاریخ انتشار 2014