[en] We present a new structurally determined seven-coordinate iron platform supported by the tris(2picolyl)amine ligand 6,60 -(pyridin-2-ylmethylazanediyl)bis(methylene)bis(N-tert-butylpicolinamide) (TPA 2C(O)NHtBu, 3) and its reactivity with oxo and nitrene transfer agents. Oxidation of the pentagonal bipyramidal, seven-coordinate iron(II)–triflate complex [TPA 2C(O)NHtBuFeII(OTf)][OTf] (4) with PhIO produces the corresponding diiron(III) l-oxo complex [(TPA 2C(O)NHtBuFeIII) 2(O)][OTf]4 (5). Mossbauer and magnetic measurements on 5 in the solid-state establish antiferromagnetic coupling between its two Fe(III) centers. Reactions of 4 with the nitrene transfer agents PhINTs (Ts = p-MeC6H4SO2) and PhINNs (Ns = p-NO2C6H4SO2) provide the corresponding iron(III)-amide congeners [TPA 2C(O)NHtBuFeIII(NHTs)][OTf]2 (6) and [TPA 2C(O)NHtBuFeIII(NHNs)][OTf] 2 (7), respectively, affording a rare pair of isolable Fe(III)-amide compounds formed from nitrene transfer. By characterizing well-defined products in the crystalline form, derived from atom and group transfer to seven-coordinate iron, the collective data provide a starting point for the exploration of high-valent and metal–ligand multiply bonded species supported by approximate pentagonal-type ligand fields.
Disciplines :
Chemistry
Author, co-author :
Soo, Han Sen; Berkeley University of California - UC Berkeley > Chemistry
Sougrati, Moulay T; University of Liege > Physics
Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique
Long, Gary J.; Missouri University of Science and Technology > Chemistry
Chang, Christopher J; Berkeley University of California - UC Berkeley > Chemistry
Language :
English
Title :
A Seven-Coordinate Iron Platform and its Oxo and Nitrene Reactivity
Alternative titles :
[en] Une plateforme de fer de coordinance sept et sa réactivité avec l'oxygène et l'azote
J. Bautz, M.R. Bukowski, M. Kerscher, M. Stubna, P. Comba, A. Lienke, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 45 2006 5681
M.R. Bukowski, K.D. Koehntop, A. Stubna, E.L. Bominaar, J.A. Halfen, E. Münck, W. Nam, and L. Que Jr. Science 310 2005 1000
M. Costas, M.P. Mehn, M.P. Jensen, and L. Que Jr. Chem. Rev. 104 2004 939
J. England, Y. Guo, E.R. Farquhar, V.G. Young Jr., E. Münck, and L. Que Jr. J. Am. Chem. Soc. 132 2010 8635
J. England, M. Martinho, E.R. Farquhar, J.R. Frisch, E.L. Bominaar, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 48 2009 3622
M. Martinho, F. Banse, J.F. Bartoli, T.A. Mattioli, P. Battioni, O. Horner, S. Bourcier, and J.-J. Girerd Inorg. Chem. 44 2005 9592
A. Mukherjee, M. Martinho, E.L. Bominaar, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 48 2009 1780
L. Que Jr. Acc. Chem. Res. 40 2007 493
K. Ray, J. England, A.T. Fiedler, M. Martinho, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 47 2008 8068
A. Thibon, J. England, M. Martinho, V.G. Young Jr., J.R. Frisch, R. Guillot, J.-J. Girerd, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 47 2008 7064
W. Nam Acc. Chem. Res. 40 2007 522
C.V. Sastri, J. Lee, K. Oh, Y.J. Lee, J. Lee, T.A. Jackson, K. Ray, H. Hirao, W. Shin, J.A. Halfen, J. Kim, L. Que Jr., and S. Shaik Proc. Natl. Acad. Sci. USA 104 2007 19181
A.S. Borovik Acc. Chem. Res. 38 2005 54
A. Dey, R.K. Hocking, P. Larsen, A.S. Borovik, K.O. Hodgson, B. Hedman, and E.I. Solomon J. Am. Chem. Soc. 128 2006 9825
R.L. Shook, and A.S. Borovik Chem. Commun. 2008 2008 6095
M.K. Zart, D. Powell, and A.S. Borovik Inorg. Chim. Acta 360 2007 2397
F.T. de Oliveira, A. Chanda, D. Banerjee, X. Shan, S. Mondal, L. Que Jr., E.L. Bominaar, E. Münck, and T.J. Collins Science 315 2007 835
C.A. Grapperhaus, B. Mienert, E. Bill, T. Weyhermüller, and K. Wieghardt Inorg. Chem. 39 2000 5306
C.E. MacBeth, A.P. Golombek, V.G. Young, C. Yang, K. Kuczera, M.P. Hendrich, and A.S. Borovik Science 289 2000 938
M. Aliaga-Alcalde, S.D. George, B. Mienert, E. Bill, K. Wieghardt, and F. Neese Angew. Chem., Int. Ed. 44 2005 2908
J.F. Berry, E. Bill, E. Bothe, S.D. George, B. Mienert, F. Neese, and K. Wieghardt Science 312 2006 1937
T. Justel, M. Muller, T. Weyhermuller, C. Kressl, E. Bill, P. Hildebrandt, M. Lengen, M. Grodzicki, A.X. Trautwein, B. Nuber, and K. Wieghardt Chem. Eur. J. 5 1999 793
K. Meyer, E. Bill, B. Mienert, T. Weyhermuller, and K. Wieghardt J. Am. Chem. Soc. 121 1999 4859
T. Petrenko, S.D. George, N. Aliaga-Alcalde, E. Bill, B. Mienert, Y. Xiao, Y. Guo, W. Sturhahn, S.P. Cramer, K. Wieghardt, and F. Neese J. Am. Chem. Soc. 129 2007 11053
J.S. Jeremiah, A.Y. Jessica, P.B. Ranko, and J.M. Smith Angew. Chem., Int. Ed. 121 2009 3204
J.J. Scepaniak, M.D. Fulton, R.P. Bontchev, E.N. Duesler, M.L. Kirk, and J.M. Smith J. Am. Chem. Soc. 130 2008 10515
C. Vogel, F.W. Heinemann, J. Sutter, C. Anthon, and K. Meyer Angew. Chem., Int. Ed. 47 2008 2681
T.A. Betley, and J.C. Peters J. Am. Chem. Soc. 126 2004 6252
M.P. Hendrich, W. Gunderson, R.K. Behan, M.T. Green, M.P. Mehn, T.A. Betley, and C.C. Lu Proc. Natl. Acad. Sci. USA 103 2006 17107
J.U. Rohde, T.A. Betley, T.A. Jackson, C.T. Saouma, J.C. Peters, and L. Que Jr. Inorg. Chem. 46 2007 5720
S.D. Brown, and J.C. Peters J. Am. Chem. Soc. 127 2005 1913
S.D. Brown, T.A. Betley, and J.C. Peters J. Am. Chem. Soc. 125 2003 322
M.P. Mehn, S.D. Brown, D.M. Jenkins, J.C. Peters, and L. Que Jr. Inorg. Chem. 45 2006 7417
C.M. Thomas, N.P. Mankad, and J.C. Peters J. Am. Chem. Soc. 128 2006 4956
I. Nieto, F. Ding, R.P. Bontchev, H.B. Wang, and J.M. Smith J. Am. Chem. Soc. 130 2008 2716
E.J. Klinker, T.A. Jackson, M.P. Jensen, A. Stubna, G. Juhász, E.L. Bominaar, E. Münck, and L. Que Jr. Angew. Chem., Int. Ed. 45 2006 7394
A.K. Verma, T.N. Nazif, C. Achim, and S.C. Lee J. Am. Chem. Soc. 122 2000 11013
N.A. Eckert, S. Vaddadi, S. Stoian, R.J. Lachicotte, T.R. Cundari, and P.L. Holland Angew. Chem., Int. Ed. 45 2006 6868
P.L. Holland Acc. Chem. Res. 41 2008 905
Y. Yu, A.R. Sadique, J.M. Smith, T.R. Dugan, R.E. Cowley, W.W. Brennessel, C.J. Flaschenriem, E. Bill, T.R. Cundari, and P.L. Holland J. Am. Chem. Soc. 130 2008 6624
S.K. Russell, E. Lobkovsky, and P.J. Chirik J. Am. Chem. Soc. 131 2008 36
R.L. Lucas, D.R. Powell, and A.S. Borovik J. Am. Chem. Soc. 127 2005 11596
T.A. Betley, and J.C. Peters J. Am. Chem. Soc. 125 2003 10782
H.S. Soo, A.C. Komor, A.T. Iavarone, and C.J. Chang Inorg. Chem. 48 2009 10024
K.P. Chiang, P.M. Barrett, F.Z. Ding, J.M. Smith, S. Kingsley, W.W. Brennessel, M.M. Clark, R.J. Lachicotte, and P.L. Holland Inorg. Chem. 48 2009 5106
S.A. Stoian, J.M. Smith, P.L. Holland, E. Münck, and E.L. Bominaar Inorg. Chem. 47 2008 8687
S.C. Bart, K. Chlopek, E. Bill, M.W. Bouwkamp, E. Lobkovsky, F. Neese, K. Wieghardt, and P.J. Chirik J. Am. Chem. Soc. 128 2006 13901
S.C. Bart, E. Lobkovsky, E. Bill, K. Wieghardt, and P.J. Chirik Inorg. Chem. 46 2007 7055
A.C. Bowman, C. Milsmann, C.C.H. Atienza, E. Lobkovsky, K. Wieghardt, and P.J. Chirik J. Am. Chem. Soc. 132 2010 1676
P.J. Chirik, and K. Wieghardt Science 327 2010 794
S.K. Russell, J.M. Darmon, E. Lobkovsky, and P.J. Chirik Inorg. Chem. 49 2010 2782
B.M. Wile, R.J. Trovitch, S.C. Bart, A.M. Tondreau, E. Lobkovsky, C. Milsmann, E. Bill, K. Wieghardt, and P.J. Chirik Inorg. Chem. 48 2008 4190
W.A. Merrill, T.A. Stich, M. Brynda, G.J. Yeagle, J.C. Fettinger, R. De Hont, W.M. Reiff, C.E. Schulz, R.D. Britt, and P.P. Power J. Am. Chem. Soc. 131 2009 12693
W.M. Reiff, A.M. LaPointe, and E.H. Witten J. Am. Chem. Soc. 126 2004 10206
W.M. Reiff, C.E. Schulz, M.-H. Whangbo, J.I. Seo, Y.S. Lee, G.R. Potratz, C.W. Spicer, and G.S. Girolami J. Am. Chem. Soc. 131 2008 404
R.L. Lucas, M.K. Zart, J. Murkerjee, T.N. Sorrell, D.R. Powell, and A.S. Borovik J. Am. Chem. Soc. 128 2006 15476
D.E. Freedman, W.H. Harman, T.D. Harris, G.J. Long, C.J. Chang, and J.R. Long J. Am. Chem. Soc. 132 2010 1224
W.H. Harman, and C.J. Chang J. Am. Chem. Soc. 129 2007 15128
W.H. Harman, T.D. Harris, D.E. Freedman, H. Fong, A. Chang, J.D. Rinehart, A. Ozarowski, M.T. Sougrati, F. Grandjean, G.J. Long, J.R. Long, and C.J. Chang J. Am. Chem. Soc. 132 2010 18115
E.R. King, and T.A. Betley Inorg. Chem. 48 2009 2361
E.R. King, and T.A. Betley J. Am. Chem. Soc. 131 2009 14374
G.T. Sazama, and T.A. Betley Inorg. Chem. 49 2010 2512
S. Gosiewska, H.P. Permentier, A.P. Bruins, G. Koten, and R. Gebbink Dalton Trans. 2007 2007 3365
G.-F. Liu, M. Filipovic, F.W. Heinemann, and I. Ivanovic-Burmazovic Inorg. Chem. 46 2007 8825
J.K. Maurin, W. Lasek, A. Górska, T. Świtaj, A.B. Jakubowska, and Z. Kazimierczuk Chem. Biodiversity 1 2004 1498
D.F. Evans J. Chem. Soc. 1959 2003
C. Piguet J. Chem. Educ. 74 1997 815
K. De Buysser, G.G. Herman, E. Bruneel, S. Hoste, and I. Van Driessche Chem. Phys. 315 2005 286
G.A. Bain, and J.F. Berry J. Chem. Educ. 85 2008 532
C. Brewer, G. Brewer, R.J. Butcher, E.E. Carpenter, L. Cuenca, B.C. Noll, W.R. Scheidt, C. Viragh, P.Y. Zavalij, and D. Zielaski Dalton Trans. 2006 2006 1009
