Iron(II) Complexes of a Hemilabile SNS Amido Ligand: Synthesis, Characterization, and Reactivity.

We report an easily prepared bis(thioether) amine ligand, SMeNHSMe, along with the synthesis, characterization, and reactivity of the paramagnetic iron(II) bis(amido) complex, [Fe(κ3-SMeNSMe)2] (1). Binding of the two different thioethers to Fe generates both five- and six-membered rings with Fe-S bonds in the five-membered rings (av 2.54 Å) being significantly shorter than those in the six-membered rings (av 2.71 Å), suggesting hemilability of the latter thioethers. Consistent with this hypothesis, magnetic circular dichroism (MCD) and computational (TD-DFT) studies indicate that 1 in solution contains a five-coordinate component [Fe(κ3-SMeNSMe)(κ2-SMeNSMe)] (2). This ligand hemilability was demonstrated further by reactivity studies of 1 with 2,2'-bipyridine, 1,2-bis(dimethylphosphino)ethane, and 2,6-dimethylphenyl isonitrile to afford iron(II) complexes [L2Fe(κ2-SMeNSMe)2] (3-5). Addition of a Brønsted acid, HNTf2, to 1 produces the paramagnetic, iron(II) amine-amido cation, [Fe(κ3-SMeNSMe)(κ3-SMeNHSMe)](NTf2) (6; Tf = SO2CF3). Cation 6 readily undergoes amine ligand substitution by triphos, affording the 16e- complex [Fe(κ2-SMeNSMe)(κ3-triphos)](NTf2) (7; triphos = bis(2-diphenylphosphinoethyl)phenylphosphine). These complexes are characterized by elemental analysis; 1H NMR, Mössbauer, IR, and UV-vis spectroscopy; and single-crystal X-ray diffraction. Preliminary results of amine-borane dehydrogenation catalysis show complex 7 to be a selective and particularly robust precatalyst.

Mononuclear, Dinuclear, and Trinuclear Iron Complexes Featuring a New Monoanionic SNS Thiolate Ligand.

The new tridentate ligand, S(Me)N(H)S = 2-(2-methylthiophenyl)benzothiazolidine, prepared in a single step from commercial precursors in excellent yield, undergoes ring-opening on treatment with Fe(OTf)2 in the presence of base affording a trinuclear iron complex, [Fe3(µ2-S(Me)NS(-))4](OTf)2 (1) which is fully characterized by structural and spectroscopic methods. X-ray structural data reveal that 1 contains four S(Me)NS(-) ligands meridionally bound to two pseudooctahedral iron centers each bridged by two thiolates to a distorted tetrahedral central iron. The combined spectroscopic (UV-vis, Mössbauer, NMR), magnetic (solution and solid state), and computational (DFT) studies indicate that 1 includes a central, high-spin Fe(II) (S = 2) with two low-spin (S = 0) peripheral Fe(II) centers. Complex 1 reacts with excess PMePh2, CNxylyl (2,6-dimethylphenyl isocyanide), and P(OMe)3 in CH3CN to form diamagnetic, thiolate-bridged, dinuclear Fe(II) complexes {[Fe(µ-S(Me)NS(-))L2]2}(OTf)2 (2-4). These complexes are characterized by elemental analysis; (1)H NMR, IR, UV-vis, and Mössbauer spectroscopy; and single crystal X-ray diffraction. Interestingly, addition of excess P(OMe)3 to complex 1 in CH2Cl2 produces primarily the diamagnetic, mononuclear Fe(II) complex, {Fe(S(Me)NS(-))[P(OMe)3]3}(OTf) (5).

Synthesis and structure of mono-, bi- and trimetallic amine-bis(phenolate) cobalt(II) complexes.

A series of cobalt(ii) amine-bis(phenolate) complexes has been prepared and characterized. The protonated tripodal tetradentate ligand precursors; dimethylaminoethylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol), H(2)[O(2)NN'](BuMeNMe2), dimethylaminoethylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol), H(2)[O(2)NN'](BuBuNMe2), diethylaminoethylamino-N,N-bis(2-methylene-4,6-di-tert-amylphenol), H(2)[O(2)NN'](AmAmNEt2) and 2-pyridylamino-N,N-bis(2-methylene-4,6-di-tert-amylphenol), H(2)[O(2)NN'](AmAmPy); were reacted with cobaltous acetate tetrahydrate under varying conditions to afford a range of monometallic, bimetallic and trimetallic species. An unusual four coordinate complex Co[O(2)NN'](AmAmNEt2) containing Co(II) in a trigonal monopyramidal environment was structurally characterized, whereas using a less sterically demanding ligand a series of five coordinate complexes Co[O(2)NN'](BuBuNMe2)(L) (L = H(2)O, CH(3)OH, (CH(3))(2)C[double bond, length as m-dash]O, propylene oxide) containing Co(II) in a trigonal bipyramidal environment was prepared. A new angular structural parameter related to tau is defined, where tau' may be used to compare complexes with trigonal monopyramidal structures. In contrast, ligands containing a pendant pyridyl donor afford dimeric species including {Co(mu-CH(3)OH)[O(2)NN'](AmAmPy)}(2). In the absence of base and in the presence of excess cobaltous acetate, trimetallic complexes were isolated containing a central Co(II) in an octahedral environment coordinated to four CH(3)OH and two bridging acetate ligands between two Co[O(2)NN'] fragments with Co(II) in a trigonal bipyramidal setting. The paramagnetic Co(II) complexes reported were also characterized by UV-vis spectroscopy, mass spectrometry, cyclic voltammetry and magnetic measurements.