Synthetic analogs for the MoFe3S3 subunit of the nitrogenase cofactor: Structural features associated with the total number of valence electrons and the possible role of M-M and multiple M-S bonding in the function of nitrogenase [17]

Journal of the American Chemical Society

Volumn 121, Issue 44, 1999, Pages 10448-10449

  Han, Jaehong ^a   Beck, Karsten ^a   Ockwig, Nathan ^a   Coucouvanis, Dimitri ^a  

^a UNIVERSITY OF MICHIGAN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MOLYBDENUM; NITROGENASE;

CHEMICAL STRUCTURE; ELECTRON; LETTER; SYNTHESIS;

EID: 0033544363     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991880o     Document Type: Letter

References (31)

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4. 1d
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15. 4-cat = tetrachlorocatecholate dianion.
16. 8a
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18. This compound was obtained using a synthetic procedure analogous to that used in the synthesis of I. (See Supporting Information).
19. For III, IR (KBr); CO region: 2021(vs), 1987(vs), 1974(m), 1958(s), 1928(s).
20. Only poorly defined, irreversible voltammetric waves could be obtained between +1.5 and -1.5 V. This behavior is not surprising, considering the profound structural changes that accompany changes in the total electron count.
21. For IV, IR (KBr); CO region: 2026(s), 2005(s), 1975(s), 1945(vs), 1891(m).
22. Elemental analyses, spectroscopic data, and crystal data for compounds III, IV, and VII have been deposited as Supporting Information.
23. The synthesis of VII from V was accomplished by the addition of trimethylamine-N-oxide to a solution of V in toluene. IR v-CO for VII: 2043-(vs), 2034(s), 2019(s), 2000(vs), 1980(s), 1968(s), 1943(m); n-Mo=O: 931-(m).
24. The electron count for VII (and VI) considers the sulfide ligand trans to the Mo=O group as an eight-electron donor. This is based on this ligand, S(2), forming three "regular" bonds to the three Fe atoms (mean S(2)-Fe bond length, 2.300(8) Å) and a long bond to the Mo atom (2.637(2) Å).
25. The individual Mo-Fe distances in VII are similar to those in VI.
26. Coucouvanis, D. Adv. Inorg. Chem. 1998, 45, 1-73.
27. One of the Fe atoms in III is coordinated by two carbonyl ligands.
28. 21
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31. 18