Modulation of the electronic structure and the Ni–Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase
10.1073/pnas.0505779102
Crossref journal-article
Proceedings of the National Academy of Sciences
Proceedings of the National Academy of Sciences (341)
Abstract

Reaction of the mononuclear Ni(II) thiolate complexes [Ni(L)] [L, L 1 , H 2 L 1 , bis(2-mercaptoethyl)-1,2-dimercaptoethane; L 2 , H 2 L 2 , N , N ′-dimethyl- N , N ′-bis(2-mercaptoethyl)-bis(aminoethyl)sulfide] with [FeCp(CO) 2 I] gives the dithiolate-bridged heterobimetallic species, [Ni(L 1 )FeCp(CO)]PF 6 , 1, and [Ni(L 2 )FeCp]I, 2, respectively. Binding of a Fe(CO) 3 fragment via reaction of square-planar [Ni(pdt)(dppe)] (dppe, 1,2-diphenylphosphinoethane; pdt 2– , 1,3-propanedithiolate) with Fe 3 (CO) 12 or [Fe(CO) 3 (BDA)] (BDA, benzylidene acetone) affords diamagnetic [(dppe)Ni(μ-pdt)Fe(CO) 3 ], 3, in which the Ni(II) center is bound tetrahedrally to two thiolate S-donors and to two P-donors. The complex [(dppe)Ni(μ-pdt)Fe(CO) 3 ], 3, reacts in solution via rearrangement to afford [(OC)Ni(μ-dppe)(μ-pdt)Fe(CO) 2 ], 4, in which one P-donor of dppe is bound to Ni and the other to Fe, and a CO ligand has transferred from Fe to Ni. Additionally, the syntheses of 3 and 4 afford the side products [(dppe)Ni(CO) 2 ] and [(OC) 3 Fe(pdt)Fe(CO) 3 ] together with the trinuclear species [(dppe)(CO)Fe(μ-CO)(μ-pdt)Fe(μ-pdt)Fe(CO) 3 ], 5. Reaction of [Ni(pdt)(dppe)] with [FeCp(CO) 2 I] in CH 2 Cl 2 affords two products [(dppe)Ni(μ-pdt)FeCp(CO)]PF 6 , 6, and [(dppe)Ni(pdt)(μ-I)Ni(dppe)]PF 6 , 7. The complexes 2, 3, and 4 show Ni–Fe distances of 2.539(4), 2.4666(6), and 2.4777(7) Å, respectively, with relatively acute dihedral angles of 79.5–81.8° for the Ni–S 2 -Fe bridge, thus mimicking the shortened Ni...Fe distance (2.5 Å) and the acute dihedral angle of the Ni–S 2 –Fe moiety observed in certain active forms of [NiFe]hydrogenase. The role of direct Ni–Fe bonding in these complexes is discussed and linked to electronic structure calculations on [(dppe)Ni(pdt)Fe(CO) 3 ], 3, which confirm the presence of a bent Ni(d z 2 )-Fe(d z 2 ) σ-bond in a singlet ground state.

Bibliography

Zhu, W., Marr, A. C., Wang, Q., Neese, F., Spencer, D. J. E., Blake, A. J., Cooke, P. A., Wilson, C., & Schröder, M. (2005). Modulation of the electronic structure and the Ni–Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase. Proceedings of the National Academy of Sciences, 102(51), 18280–18285.

Authors 9
  1. Wenfeng Zhu (first)
  2. Andrew C. Marr (additional)
  3. Qiang Wang (additional)
  4. Frank Neese (additional)
  5. Douglas J. E. Spencer (additional)
  6. Alexander J. Blake (additional)
  7. Paul A. Cooke (additional)
  8. Claire Wilson (additional)
  9. Martin Schröder (additional)
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Dates
Type When
Created 19 years, 8 months ago (Dec. 13, 2005, 9:38 p.m.)
Deposited 3 years, 4 months ago (April 12, 2022, 10:21 a.m.)
Indexed 11 months, 1 week ago (Sept. 15, 2024, 3:10 p.m.)
Issued 19 years, 8 months ago (Dec. 13, 2005)
Published 19 years, 8 months ago (Dec. 13, 2005)
Published Online 19 years, 8 months ago (Dec. 13, 2005)
Published Print 19 years, 8 months ago (Dec. 20, 2005)
Funders 0

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@article{Zhu_2005, title={Modulation of the electronic structure and the Ni–Fe distance in heterobimetallic models for the active site in [NiFe]hydrogenase}, volume={102}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0505779102}, DOI={10.1073/pnas.0505779102}, number={51}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Zhu, Wenfeng and Marr, Andrew C. and Wang, Qiang and Neese, Frank and Spencer, Douglas J. E. and Blake, Alexander J. and Cooke, Paul A. and Wilson, Claire and Schröder, Martin}, year={2005}, month=dec, pages={18280–18285} }