Modeling the cis-oxo-labile binding site motif of non-heme iron oxygenases: water exchange and oxidation reactivity of a non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand.
The spectroscopic and chemical characterization of a new synthetic non-heme iron(IV)-oxo species [Fe(IV)(O)((Me,H) Pytacn)(S)](2+) (2, (Me,H)Pytacn=1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, S=CH(3)CN or H(2)O) is described. Complex 2 was prepared by reaction of [Fe(II)(CF(3)SO(3))(2)((Me,H) Pytacn)] (1) with peracetic acid. Complex 2 bears a tetradentate N(4) ligand that leaves two cis sites available for binding an oxo group and a second external ligand but, unlike the related iron(IV)-oxo species with tetradentate ligands, it is remarkably stable at room temperature (t(1/2)>2 h at 288 K). Its ability to exchange the oxygen atom of the oxo ligand with water has been analyzed in detail by means of kinetic studies, and a mechanism is proposed on the basis of DFT calculations. Hydrogen-atom abstraction from C-H bonds and oxygen-atom transfer to sulfides by 2 have also been studied. Despite its thermal stability, 2 proves to be a very powerful oxidant that is capable of breaking the strong C-H bond of cyclohexane (bond dissociation energy=99.3 kcal mol(-1)).
Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia, Spain.
Anna
A
Company
Irene
I
Prat
Jonathan R
JR
Frisch
Ruben
R
Mas-Ballesté
Mireia
M
Güell
Gergely
G
Juhász
Xavi
X
Ribas
Eckard
E
Münck
Josep M
JM
Luis
Lawrence
L
Que
Miquel
M
Costas
D001665:Binding Sites; D018360:Crystallography, X-Ray; D006418:Heme / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D008024:Ligands; D008956:Models, Chemical; D015394:Molecular Structure; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000737:chemistry*; D013816:Thermodynamics
D058085:Iron Compounds; D008024:Ligands; D016877:Oxidants; D006418:Heme; D007501:Iron; D010105:Oxygenases
J Am Chem Soc. 2007 Nov 7;129(44):13408-9
17939667
J Am Chem Soc. 2009 Apr 29;131(16):5823-30
19338307
J Am Chem Soc. 2003 Oct 29;125(43):13008-9
14570457
Biochemistry. 2003 Jun 24;42(24):7497-508
12809506
J Am Chem Soc. 2005 Jul 13;127(27):9904-12
15998097
Inorg Chem. 2006 Jun 26;45(13):5119-25
16780334
J Am Chem Soc. 2004 Jan 21;126(2):472-3
14719937
J Am Chem Soc. 2010 Jun 30;132(25):8635-44
20568768
Angew Chem Int Ed Engl. 2008;47(38):7321-4
18683830
J Am Chem Soc. 2010 Jan 27;132(3):1087-97
20041691
Inorg Chem. 2008 Jan 7;47(1):78-93
18072762
Science. 2005 Nov 11;310(5750):1000-2
16254150
J Am Chem Soc. 2010 Jun 9;132(22):7638-44
20476758
Inorg Chem. 2007 May 28;46(11):4632-41
17444641
Angew Chem Int Ed Engl. 2004 Apr 26;43(18):2417-20
15114578
J Am Chem Soc. 2005 Sep 14;127(36):12494-5
16144389
Proc Natl Acad Sci U S A. 2007 Dec 4;104(49):19181-6
18048327
Inorg Chem. 2005 Apr 4;44(7):2150-8
15792449
Proc Natl Acad Sci U S A. 2006 Oct 3;103(40):14738-43
17003127
Angew Chem Int Ed Engl. 2008;47(42):8068-71
18798182
Angew Chem Int Ed Engl. 2006 Aug 25;45(34):5681-4
16858708
Chem Rev. 2000 Jan 12;100(1):235-350
11749238
Angew Chem Int Ed Engl. 2006 Jun 12;45(24):3992-5
16688689
Proc Natl Acad Sci U S A. 2003 Apr 1;100(7):3665-70
12644707
Angew Chem Int Ed Engl. 2005 Jun 13;44(24):3690-4
15915527
J Am Chem Soc. 2006 Mar 1;128(8):2630-4
16492048
J Am Chem Soc. 2010 Sep 8;132(35):12188-90
20704272
Inorg Chem. 2010 Jun 7;49(11):4759-61
20446674
J Am Chem Soc. 2005 Aug 3;127(30):10512-25
16045338
J Am Chem Soc. 2002 Jan 9;124(1):83-96
11772065
J Am Chem Soc. 2005 Mar 30;127(12):4178-9
15783193
J Am Chem Soc. 2008 Jun 25;130(25):7776-7
18512909
J Am Chem Soc. 2001 Jul 4;123(26):6327-37
11427057
Angew Chem Int Ed Engl. 2009;48(20):3622-6
19373820
Inorg Chem. 2003 Sep 22;42(19):5974-88
12971768
J Chem Phys. 2010 Apr 21;132(15):154104
20423165
Science. 1995 Sep 29;269(5232):1849-51
7569922
Angew Chem Int Ed Engl. 2005 Jul 4;44(27):4235-9
15937890
Chemistry. 2009 Dec 14;15(48):13435-40
19876973
J Am Chem Soc. 2004 Dec 29;126(51):16750-61
15612713
Chemistry. 2009 Nov 2;15(43):11482-9
19810056
J Am Chem Soc. 2006 Jul 5;128(26):8590-606
16802826
J Biol Chem. 2003 Jan 10;278(2):829-35
12403773
Chemistry. 2008;14(19):5727-31
18481345
Inorganica Chim Acta. 2008 Mar 3;361(4):973-986
19262682
Acc Chem Res. 2007 Jul;40(7):493-500
17595051
Chem Commun (Camb). 2005 Mar 21;(11):1405-7
15756318
Chem Rev. 2005 Jun;105(6):2227-52
15941213
J Am Chem Soc. 2007 Oct 17;129(41):12390-1
17894497
Science. 2003 Feb 14;299(5609):1037-9
12586936
J Am Chem Soc. 2003 Aug 27;125(34):10351-61
12926960
J Comput Chem. 2006 Sep;27(12):1292-306
16786546
J Am Chem Soc. 2007 Sep 19;129(37):11334-5
17715926
Angew Chem Int Ed Engl. 2010 Mar 29;49(14):2622-5
20229541
J Am Chem Soc. 2007 Dec 26;129(51):15766-7
18052284
J Am Chem Soc. 2004 Jul 7;126(26):8108-9
15225039
J Biol Inorg Chem. 2006 Apr;11(3):272-6
16532334
Angew Chem Int Ed Engl. 2006 May 19;45(21):3446-9
16637091
J Am Chem Soc. 2008 Nov 12;130(45):15134-42
18937476
J Am Chem Soc. 2007 Feb 14;129(6):1512-3
17249671
Angew Chem Int Ed Engl. 2009;48(7):1291-5
19130517
Biochemistry. 1996 Aug 6;35(31):10240-7
8756490
Inorg Chem. 2008 Apr 21;47(8):2975-86
18366153
Nat Chem Biol. 2007 Feb;3(2):113-6
17220900
Angew Chem Int Ed Engl. 2005 Oct 28;44(42):6871-4
16206322
Angew Chem Int Ed Engl. 2007;46(42):8067-70
17868164
J Am Chem Soc. 2004 Feb 4;126(4):1022-3
14746461
Phys Rev Lett. 1996 Oct 28;77(18):3865-3868
10062328
Angew Chem Int Ed Engl. 2008;47(37):7064-7
18677790
Chem Rev. 2004 Feb;104(2):939-86
14871146
J Am Chem Soc. 2005 Jun 8;127(22):8026-7
15926822
Biochemistry. 2009 May 26;48(20):4331-43
19245217
Acc Chem Res. 2007 Jul;40(7):522-31
17469792
Angew Chem Int Ed Engl. 2009;48(7):1257-60
19137521
Nat Chem. 2010 May;2(5):400-5
20414242
Chem Rev. 2010 Feb 10;110(2):1060-81
20143877
Nat Chem. 2009 May;1(2):145-50
19885382
J Am Chem Soc. 2002 Aug 28;124(34):10112-23
12188675
Angew Chem Int Ed Engl. 2008;47(10):1896-9
18228548
Inorg Chem. 2005 Dec 12;44(25):9592-6
16323949