The Münck Group

Home     Group     Research     Publications     Collaborator Info     Contact


Emile L. Bominaar     

Research Interests

(1)    Theory of mono- and polynuclear transition metal complexes and metalloproteins

(2)    Application and development of spectroscopic tools for the study of TM centers


Department of Chemistry
Carnegie Mellon University
4400 Fifth Avenue
Pittsburgh, PA 15213
Telephone    (412) 268 5671

Domestic Duties

Publications by subject:

(1) Iron-sulfur clusters (refs 25-28, 30, 32, 38, 40, 43, 49, 53, 54, 57, 58, 72, 77, 78, 83)

(2) Electron transfer involving mixed-valence complexes (34-36, 41, 44, 47)

(3) Low-coordinate complexes of iron (48, 61, 62, 65, 71, 73)

(4) Oxygen activation by nonheme species (29, 55, 58, 59, 63, 67, 80-82, 85, 86)

(5) TM complexes of tetra amido macrocyclic ligands (66, 69, 70, 74, 75)

(6) Spin transitions (37, 68)

(7) Iron-gadolinium complexes (84)

(8) Disulfide conformations (76, 79)

(9) Fundamentals of spectroscopy, notably magnetic linear dichroism (42, 45, 46, 50-52, 87).

Click here for an Introduction to Optical Activity.


/87/ Münck, E.; Bominaar, E. L. 2011
“Mössbauer Spectroscopy of Biological Systems. “
In The Rudolf Mössbauer Story. G. M. Kalvius and P. Kienle (editors), Springer Verlag, in press.

/86/ M.M. Mbughuni, M. Chakrabarti, J.A. Hayden, E.L. Bominaar, M.P. Hendrich, E. Münck, J.D. Lipscomb
"Trapping and Spectroscopic Characterization of an FeIII-superoxo Intermediate from a Nonheme Mononuclear Iron-containing Enzyme."
Proc. Natl. Acad. Sci. U.S.A. 107 (2010) 16788-16793.

/85/ R.F. De Hont, G. Xue, M.P. Hendrich, L. Que, E.L. Bominaar, E. Münck
"Mössbauer, EPR and DFT Studies of Synthetic µ-oxo Bridged S = ½ FeIII-O- FeIV=O Complexes. Superexchange-mediated Spin Transition at the FeIV=O Site."
Inorg. Chem. 49 (2010) 8310-8322.

/84/ S.A. Stoian, C. Paraschiv, N. Kiritsakas, F. Lloret, E. Münck, E.L. Bominaar, M. Andruh "Mössbauer, EPR, and magnetic susceptibility studies on members of a newfamily of cyano-bridged 3d-4f complexes. Demonstration of anisotropic exchange in a Fe-Gd complex."
Inorg. Chem. 49 (2010) 3387-3401.

/83/ M. Chakrabarti, L. Deng, R.H. Holm, E. Munck, E.L. Bominaar
"The Modular Nature of All-Ferrous Edge-Bridged Double Cubanes."
Inorg. Chem. 49 (2010) 1647-1650.

/82/ A. Mukherjee, M. Martinho, E.L. Bominaar, E. Münck, L. Que, Jr.
"Shape-selective interception by hydrocarbons of the O2-derived oxidant of a biomimetic nonheme iron complex."
Angew. Chemie, Intl. Ed. 48 (2009) 1780-1783.

/81/ J. England, M. Martinho, E.R. Farquhar, J.R. Frisch, E.L. Bominaar, E. Münck, L. Que, Jr. "A synthetic high-spin oxoiron(IV) complex: Generation, spectroscopic characterization, and reactivity."
Angew. Chemie, Intl. Ed. 48 (2009) 3622-3626.

/80/ M. Martinho, G. Xue, A.T. Fiedler, L. Que, Jr, E.L. Bominaar, E. Münck
"Mössbauer and DFT study of the ferromagnetically coupled diiron(IV) precursor to a complex with an FeIV2O2 diamond core."
J. Am. Chem. Soc. 131 (2009) 5823–5830.

/79/ O.A. Ozhogina, E.L. Bominaar
"Characterization of the kringle fold and identification of a ubiquitous new class of rotamers."
J. Struct. Biol. 168 (2009) 223–233.

/78/ M. Chakrabarti, L. Deng, R.H. Holm, E. Münck, E.L. Bominaar
"Mössbauer, Electron paramagnetic resonance, and theoretical studies of a carbene-based all-ferrous Fe4S4 cluster: Electronic origin and structural identification of the unique spectroscopic site."
Inorg. Chem. 48 (2009) 2735–2747.

/77/ E. Münck, E.L. Bominaar
"Bringing stability to highly reduced iron-sulfur clusters"
Science 321 (2008) 1452-1453.

/76/ O.A. Ozhogina, A. Grishaev, E.L. Bominaar, L. Patthy, M. Llinas
"NMR solution structure of the neurotrypsin kringle domain"
Biochemistry 47 (2008) 12290-12298.

/75/ D.L. Popescu, A. Chanda, M. Stadler, F. Tiago de Oliveira, A.D. Ryabov, E. Münck, E.L. Bominaar, T.J. Collins
"High-valent first-row transition-metal complexes of tetraamido (4N) and diamidodialkoxido or diamidophenolato (2N/2O) ligands: synthesis, structure, and magnetochemistry."
Coord. Chem. Rev. 252 (2008) 2050-2071.

/74/ A. Chanda, F. Tiago de Oliveira, T.J. Collins, E. Münck, E.L. Bominaar
"Density functional theory study of the structural, electronic, and magnetic properties of a ?-oxo bridged dinuclear Fe(IV) complex based on a tetra-amido macrocyclic ligand."
Inorg. Chem. 47 (2008) 9372-9379.

/73/ S.A. Stoian, J.M. Smith, P.L. Holland, E. Münck, E.L. Bominaar
"Mössbauer, electron paramagnetic resonance, and theoretical study of a high-spin, four-coordinate Fe(II) diketiminate complex."
Inorg. Chem. 47 (2008) 8687-8695.

/72/ F. de Oliveira, E. Münck, E.L. Bominaar
"DFT study of the intrinsic conformations of [2Fe-2S-4(SCH3)]2- clusters and their influence on exchange coupling."
Inorg. Chim. Acta 361 (2008) 1192-1196.

/71/ V. Polshin, D.L. Popescu, A. Fischer, A. Chanda, D.C. Horner, E.S. Beach, J. Henry, Y.L. Qian, C.P. Horwitz, G. Lente, I. Fabian, E. Münck, E.L. Bominaar, A.D. Ryabov, T.J. Collins "Attaining control by design over the hydrolytic stability of Fe-TAML oxidation catalysts."
J. Am. Chem. Soc. 130 (2008) 4497-4506.

/70/ A. Chanda, X. Shan, M. Chakrabarti, W. C. Ellis, D.L. Popescu, F. Tiago de Oliveira, D. Wang, L. Que, T.J. Collins, E. Münck, E.L. Bominaar
"(TAML)FeIV=O complex in aqueous solution: Synthesis and spectroscopic and computational characterization."
Inorg. Chem. 47 (2008) 3669-3678.

/69/ F. Tiago de Oliveira, A. Chanda, D. Banerjee, X. Shan, S. Mondal, L. Que, Jr., E.L. Bominaar, E. Münck, T.J. Collins
"Chemical and spectrocopic evidence for an FeV-oxo complex."
Science 2007, 315, 835-838.

/68/ M. Shatruk, A. Dragulescu-Andrasi, K.E. Chambers, S.A. Stoian, E.L. Bominaar, C. Achim, K.R. Dunbar
"Properties of prussian blue materials manifested in molecular complexes: Observation of cyanide linkage isomerism and spin-crossover behavior in pentanuclear cyanide clusters."
J. Am. Chem. Soc. 129 (2007) 6104-6116.

/67/ E.J. Klinker, T.A. Jackson, M.P. Jensen, A. Stubna, G. Juhasz, E.L. Bominaar, E. Münck, L. Que,
"A tosylimido analogue of a nonheme oxoiron(IV) complex."
Angew. Chemie, Intl. Ed. 45 (2006) 7394-7397.

/66/ A. Chanda, D. Popescu, F. Tiago de Oliviera, E.L. Bominaar, A. Ryabov, E. Münck, T.J. Collins
"High valent iron complexes with tetraamido macrocyclic ligands: structures, Mössbauer spectroscopy, and DFT calculations."
J. Inorg. Biochemistry 100 (2006) 606-619.

/65/ S.A. Stoian, J. Vela, J.M. Smith, A.R. Sadique, P.L. Holland, E. Munck, E.L. Bominaar
"Mössbauer and Computational Study of an N2-Bridged Diiron Diketiminate Complex: Parallel Alignment of the iron spins by direct antiferromagnetic exchange with activated dinitrogen"
J. Am. Chem. Soc. 128 (2006) 10181-10192.

/64/ J. Jullien, G. Juhasz, P. Mialane, E. Dumas, C.R. Mayer, J. Marrot, E. Riviere, E.L. Bominaar, E. Munck, F. Secheresse
"Structure and magnetic properties of a non-heme diiron complex singly bridged by a hydroxo group."
Inorg. Chem. 45 (2006) 6922-6927.

/63/ J.U. Rohde, A. Stubna, E.L. Bominaar, E. Münck, W. Nam, L. Que, Jr.
" Nonheme oxo-iron(IV) complexes of tris(2-pyridylmethyl)amine with cis-monoanionic ligands."
Inorg. Chem. 45 (2006) 6435-6445.

/62/ S.A. Stoian, Y. Yu, J.M. Smith, P.L. Holland, E.L. Bominaar, E. Münck
"Mössbauer, electron paramagnetic resonance, and crystallographic characterization of a high-spin Fe(I) diketiminate complex with orbital degeneracy."
Inorg. Chem. 44 (2005) 4915-4922.

/61/ N.A. Eckert, S. Stoian, J.M. Smith, E.L. Bominaar, E. Münck, P.L. Holland
"Synthesis, structure, and spectroscopy of an oxodiiron(II) complex."
J. Am. Chem. Soc. 127 (2005) 9344-9345.

/60/ M.V. Bennett, S. Stoian, E.L. Bominaar, E. Münck, R.H. Holm
"Initial members of the family of molecular mid-valent high-nuclearity iron nitrides: [Fe4N2X10]4- and [Fe10N8X12]5- (X = Cl-, Br-)."
J. Am. Chem. Soc. 127 (2005) 12378-12386.

/59/ M.R. Bukowski, K.D. Koehntop, A. Stubna, E.L. Bominaar, J.A. Halfen, E. Münck, W. Nam, L. Que, Jr.
"A thiolate-ligated nonheme oxoiron(IV) complex relevant to cytochrome P450."
Science 310 (2005) 1000-1002.

/58/ O. Pestovsky, S. Stoian, E.L. Bominaar, X. Shan, E. Münck, L. Que, Jr.; A. Bakac
"Aqueous FeIV=O: Spectroscopic identification and oxo-group exchange."
Angew. Chemie, Intl. Ed. 44 (2005) 6871-6874.

/57/ V.V. Vrajmasu, E. Münck, E.L. Bominaar
“Theoretical analysis of the Jahn-Teller distortions in tetrathiolato iron(II) complexes”
Inorg. Chem. 43 (2004) 4862-4866.

/56/ V.V. Vrajmasu, E. Münck, E.L. Bominaar
“Theoretical analysis of the three-dimensional structure of tetrathiolato iron complexes.” Inorg. Chem. 43 (2004) 4867-4879.

/55/ A. Stubna, D.H. Jo, M. Costas, M. Brenessel, H.P. Andres, E.L. Bominaar, E. Münck, L. Que, Jr.
“A structural and Mössbauer study of complexes with Fe2(?-O(H))2 cores: Stepwise oxidation from FeII(?-OH)2FeII through FeII(?-OH)2FeIII to FeIII((?O)( ?-OH)FeIII.”
Inorg. Chem. 43 (2004) 3067-3079.

/54/ F. Tiago de Oliveira, E.L. Bominaar, J. Hirst, J.A. Fee, E. Münck
“Antisymmetric Exchange in [2Fe-2S]1+ Clusters: EPR of the Rieske Protein from Thermus thermophilus at pH 14.”
J. Am. Chem. Soc. 126 (2004) 5338-5339.

/53/ V.V. Vrajmasu, E. Münck, E.L. Bominaar
"Density functional study of electric hyperfine interactions and redox-structural correlations in cofactor of nitrogenase. Analysis of general trends of 57Fe isomer shift."
Inorg. Chem. 42 (2003) 5974-5988.

/52/ L.L. Pearce, E.L. Bominaar, J. Peterson
Visible region MCD and MLD spectra of nitrosylferrohemoglobin and oxyhemoglobin. Biochemical and Biophysical Research Communications 297 (2002) 220-223.

/51/ J. Peterson, T.J. Collins, E. Münck, E.L. Bominaar
Resolution of overlapping charge-transfer transitions by a combined absorption-MCD-MLD approach.
Chem. Phys. Lett. 365 (2002) 164-169.

/50/ J. Peterson, E.L. Bominaar
Resolving molecular electronic spectra using magnetic linear dichroism.
Anal. Chem. 74 (2002) 527A-533A.

/49/ V.V. Vrajmasu, E.L. Bominaar, J. Meyer, E. Münck
Mössbauer study of reduced rubredoxin as purified and in whole cells. Structural correlation analysis of spin Hamiltonian parameters.
Inorg. Chem. 41 (2002) 6358-6371.

/48/ H.P. Andres, E.L. Bominaar, J.M. Smith, N.A. Eckert, P.L. Holland, E. Münck
Planar three-coordinate high-spin Fe(II) complexes with large orbital angular momentum: Mössbauer, electron paramagnetic resonance, and electronic structure studies.
J. Am. Chem. Soc. 124 (2002) 3012-3025.

/47/ C. Achim, E.L. Bominaar, E. Münck, R.H. Holm
Influence of extrinsic factors on electron transfer in a mixed-valence Fe2+/Fe3+ complex: Experimental results and theoretical considerations.
Inorg. Chem. 40 (2001) 4389-4403.

/46/ E.L. Bominaar, J. Peterson
Development and experimental verification of a theory for high-field, ultra-low temperature magnetic linear dichroism of glasses containing molecular chromophores with spin doublet ground states.
J. Chem. Phys. 111 (1999) 7512-7518.

/45/ J. Peterson, L.L. Pearce, E.L. Bominaar
The visible region magnetic linear dichroism spectra of ferrocytochrome c and deoxymyoglobin: Demonstration of a new tool for the study of metalloproteins.
J. Am. Chem. Soc. 121 (1999) 5972-5980.

/44/ E.L. Bominaar, C. Achim, S.A. Borshch
Theory for electron transfer from a mixed-valence dimer with paramagnetic sites to a mononuclear acceptor.
J. Chem. Phys. 110 (1999) 11411-11422.

/43/ C. Achim, E.L. Bominaar, J. Meyer, J. Peterson, E. Münck
Observation and interpretation of temperature-dependent valence delocalization in the [2Fe-2S]+ cluster of a ferredoxin from Clostridium pasteurianum.
J. Am. Chem. Soc. 121 (1999) 3704-3714.

/42/ E.L. Bominaar, C. Achim, J. Peterson
Theory for magnetic linear dichroism of electronic transitions between twofold-degenerate molecular spin levels.
J. Chem. Phys. 109 (1998) 942-950.

/41/ C. Achim, E.L. Bominaar, E. Münck
Aspects of valence delocalization relevant to the kinetic properties of electron-transfer chains.
J. Biol. Inorg. Chem. 3 (1998) 126-134.

/40/ C. Goh, A. Nivorozhkin, S.J. Yoo, E.L. Bominaar, E. Münck, R.H. Holm
The mixed-valence double-cubanoid cluster [Fe8S12(ButNC]12]: Synthesis, Structure, and exchange coupling of a new structural array of four Fe(III) sites.
Inorg. Chem. 37 (1998) 2926-2932.

/39/ P. Mialane, E. Anxalobéhère-Mallart, G. Blondin, A. Nivorojkine, J. Guilhem, L. Tchertanova, M. Cesario, N. Ravi, E.L. Bominaar, J.-J. Girerd, E. Münck
Structure and electronic properties of (N,N’-bis(4-methyl-6-tert-butyl-2-methyl-phenolato)-N,N’-bismethyl-1,2-diaminoethane)FeIII(DBSQ). Spectroelectrochemical study of the redox properties . Relevance to intradiol catechol dioxygenases.
Inorg. Chim. Acta 263 (1997) 367-378.

/38/ S.J. Yoo, Z. Hu, C. Goh, E.L. Bominaar, R.H. Holm, E. Münck
Determination of the exchange-coupling constant of an Fe3+–Fe3+ pair in a cubane-type Fe–S cluster.
J. Am. Chem. Soc. 119 (1997) 8732-8733.

/37/ T.J. Collins, S.W. Gordon-Wylie, E.L. Bominaar, C.P. Horwitz, G. Yee
Ligand design approaches for controlling exchange coupling and fabricating molecular magnetic materials.
NATO ASI Series, Series C: Mathematical and Physical Sciences, volume 484, Magnetism: a supramolecular function, ed. O. Kahn, Kluwer, Dordrecht, p. 509.

/36/ E.L. Bominaar, C. Achim, S.A. Borshch, J.-J. Girerd, E. Münck
Analysis of exchange interaction and electron delocalization as intramolecular determinants of intermolecular electron-transfer kinetics.
Inorg. Chem. 36 (1997) 3689-3701.

/35/ D.R. Gamelin, E.L. Bominaar, C. Mathonière, M.L. Kirk, K. Wieghardt, J.-J. Girerd, E.I. Solomon
Excited-state distortions and electron delocalization in mixed-valence dimers: vibronic analysis of the near-IR absorption and resonance Raman profiles of [Fe2(OH)3(tmtacn)2]2+ .
Inorg. Chem. 35 (1996) 4323-4335.

/34/ D.R. Gamelin, E.L. Bominaar, M.L. Kirk, K. Wieghardt, E.I. Solomon
Excited-state contributions to ground-state properties of mixed-valence dimers: spectral and electronic-structural studies of [Fe2(OH)3(tmtacn)2]2+ related to the [Fe2S2]+ active sites of plant-type ferredoxins.
J. Am. Chem. Soc. 118 (1996) 8085-8097.

/33/ D.H. Nguyen, H.F. Hsu, M. Millar, S.A. Koch, C. Achim, E.L. Bominaar, E. Münck
Nickel(II) thiolate complex with carbon monoxide and its Fe(II) analog: synthetic models for CO adducts of nickel–iron-containing enzymes.
J. Am. Chem. Soc. 118 (1996) 8963-8964.

/32/ C. Achim, M.-P. Golinelli, E.L. Bominaar, J. Meyer, E. Münck
Mössbauer study of Cys56Ser mutant 2Fe ferredoxin from Clostridium pasteurianum: evidence for double exchange in an [Fe2S2]+ cluster.
J. Am. Chem. Soc. 118 (1996) 8168-8169.

/31/ S.W. Gordon-Wylie, E.L. Bominaar, T.J. Collins, J.M. Workman, B.L. Claus, R.E. Patterson, S.A. Williams, B.J. Conklin, G.T. Yee, S.T. Weintraub
Ligand design for securing ferromagnetic exchange coupling in multimetallic complexes.
Chem. Eur. J. 1 (1995) 528-537.

/30/ E.L. Bominaar, Z. Hu, E. Münck, J.-J. Girerd, S. Borshch
Double exchange and vibronic coupling in mixed-valence systems. Electronic structure if exchange-coupled siroheme–[Fe4S4]2+ chromophore in oxidized E. coli sulfite reductase.
J. Am. Chem. Soc. 117 (1995) 6976-6989.

/29/ N. Ravi, E.L. Bominaar
Exchange coupling approach to the radical disposition of the intermediate in E. coli ribonucleotide reductase.
Inorg. Chem. 34 (1995) 1040-1043.

/28/ G. Blondin, E.L. Bominaar, J.-J. Girerd, S.A. Borshch
Spin dependent electron delocalization, vibronic and antiferromagnetic couplings in iron–sulfur clusters.
NATO ASI Series, Nuclear magnetic resonance of paramagnetic molecules, 1994.

/27/ E.L. Bominaar, S.A. Borshch, J.-J. Girerd
Double-exchange and vibronic coupling in mixed-valence systems. Electronic structure of [Fe4S4]3+ clusters in high-potential iron protein and related models.
J. Am. Chem. Soc. 116 (1994) 5362-5372.

/26/ S.A. Borshch, E.L. Bominaar, G. Blondin, J.-J. Girerd
Double exchange and vibronic coupling in mixed-valence systems. Origin of the broken-symmetry ground state of [Fe3S4]0 cores in proteins and models.
J. Am. Chem. Soc. 115 (1993) 5155-5168.

/25/ S.A. Borshch, E.L. Bominaar, J.-J. Girerd
Electron delocalization in four-nuclear mixed-valence clusters with para-magnetic ions.
New J. Chem. 17 (1993) 39-42.


Ref 45 quoted in C&EN July 5, 1999, page 29:


Cover page of Inorg. Chem. 2009, issue 7 (ref 78):

Spin ordering in a carbene-coordinated 4Fe–4S model complex for the all-ferrous cluster in the iron protein of nitrogenase is deduced from spectroscopic and theoretical analysis. See M. Chakrabarti, L. Deng, R. H. Holm, E. Münck, and E. L. Bominaar, p 2735.


updated 2/2011