Rational Design of Iron Spin-Crossover Complexes Using Heteroscorpionate Chelates.

The optical, structural, and magnetic properties of iron(II,III) sandwich complexes, Fe(Tp')2n+ (Tp' = bis(3,5-dimethylpyrazolyl)benzotriazolylborate), are described. The intensely colored FeII(Tp')2 (orange) and FeIII(Tp')2+ (purple) show strong MLCT bands. Geometric isomerism for M(Tp')2 is established crystallographically in the racemate of chiral cis-Fe(Tp')2. For the first time, paramagnetic 11B NMR describes solution-phase low-spin (LS, S = 0) to high-spin (HS, S = 2) crossover behavior in Fe(Tp')2. Thermochemical parameters for solution-phase SCO of Fe(Tp')2 demonstrate the endothermic LS to HS conversion and entropic preference of the HS state. Entropy changes for both Fe(Tp')2 isomers are significantly larger than for the majority of iron scorpionate SCO systems. Solid-state magnetic and thermochemical measurements show cis-Fe(Tp')2 to be thermally stable up to 520 K, allowing experimental investigation of a solid-state SCO magnetic hysteresis of over 45 K. A large solution vs solid-state SCO difference was observed: cis-Fe(Tp')2 shows Tc ≈ 270 K (solution) and Tc ≈ 385 K (solid), with the remarkably wide ΔTc ≈ 115 K; trans-Fe(Tp')2 shows Tc ≈ 278 K (solution) and Tc ≈ 372 K (solid). Solid-state Tc values are among the highest seen for iron(II) molecular systems. The large solution/solid ΔTc difference is explained by "anchoring" intermolecular interactions in the solid state that prevent thermal expansion of the LS iron(II) coordination sphere in its transition to the HS state. DFT calculations, validated against LS cis-Fe(Tp')2 crystallography and LS to HS SCO thermochemical parameters, demonstrate the role the benzotriazole rings play in its structural and optical properties. The Lewis basicity of M(Tp')2 is shown with the structural characterization of the air-stable tin(II) adduct [cis-Fe(Tp')2-SnCl2]; tin(II) coordination does not alter the iron(II) spin state. The Tp' chelate adds functionality (asymmetry, chirality, chemical reactivity) to the array of iron SCO materials for potential incorporation into nanoscale magnetic switches and spintronic devices.

Electronic structure of nickel(II) and zinc(II) borohydrides from spectroscopic measurements and computational modeling.

The previously reported Ni(II) complex, Tp*Ni(κ(3)-BH(4)) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate anion), which has an S = 1 spin ground state, was studied by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy as a solid powder at low temperature, by UV-vis-NIR spectroscopy in the solid state and in solution at room temperature, and by paramagnetic (11)B NMR. HFEPR provided its spin Hamiltonian parameters: D = 1.91(1) cm(-1), E = 0.285(8) cm(-1), g = [2.170(4), 2.161(3), 2.133(3)]. Similar, but not identical parameters were obtained for its borodeuteride analogue. The previously unreported complex, Tp*Zn(κ(2)-BH(4)), was prepared, and IR and NMR spectroscopy allowed its comparison with analogous closed shell borohydride complexes. Ligand-field theory was used to model the electronic transitions in the Ni(II) complex successfully, although it was less successful at reproducing the zero-field splitting (zfs) parameters. Advanced computational methods, both density functional theory (DFT) and ab initio wave function based approaches, were applied to these Tp*MBH(4) complexes to better understand the interaction between these metals and borohydride ion. DFT successfully reproduced bonding geometries and vibrational behavior of the complexes, although it was less successful for the spin Hamiltonian parameters of the open shell Ni(II) complex. These were instead best described using ab initio methods. The origin of the zfs in Tp*Ni(κ(3)-BH(4)) is described and shows that the relatively small magnitude of D results from several spin-orbit coupling (SOC) interactions of large magnitude, but with opposite sign. Spin-spin coupling (SSC) is also shown to be significant, a point that is not always appreciated in transition metal complexes. Overall, a picture of bonding and electronic structure in open and closed shell late transition metal borohydrides is provided, which has implications for the use of these complexes in catalysis and hydrogen storage.

Immobilized boron-centered heteroscorpionates: heterocycle metathesis and coordination chemistry.

The preparation of a resin-supported boron-scorpionate ligand and its nickel(II) coordination complexes are reported. The supported ligand is prepared as its potassium salt, making it a general reagent suitable for chelation of any transition metal ion. Resin-immobilized benzotriazole (Bead-btz) reacted cleanly with KTp* (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by heterocycle metathesis in warm dimethylformamide (DMF) to yield bead-Tp'K, {resin-btz(H)B(pz*)(2)}K. Significantly, bead-Tp'K readily bound nickel(II) from simple salts with minimal leaching of the nickel ion. Bead-Tp'NiNO(3) reacts further with cysteine thiolate (ethyl ester), imparting the deep green color to the beads characteristic of a Tp(R)NiCysEt coordination sphere. Bead-Tp'NiCysEt exhibited an oxygen sensitivity similar to Tp*NiCysEt in solution (Inorg. Chem. 1999, p 5690) and also independently verified for a selenocystamine analogue, Tp*NiSeCysAm. Addition of fresh cysteine thiolate ethyl ester to oxidized bead-Tp'NiCysEt reproduced the original green color. Heterocycle metathesis was also used to prepare KTp' as a white solid. Reaction with nickel(II) gave (Tp')(2)Ni, separable into two different isomers. The air-sensitive molybdenum(0) complex, [PPh(4)][Tp'Mo(CO)(3)], was also prepared and the C(s) complex symmetry demonstrated by infrared and (13)C NMR spectroscopies. Immobilized TpmMo(CO)(3) was prepared from the previously reported resin-supported tris(pyrazolyl)methane. In contrast to its weak coordination of nickel(II) (Inorg. Chem. 2009, p 3535), bead-Tpm proved a strong chelate toward this second row metal. The supported scorpionates described here should find use in studies of selective metal-protein binding, metalloprotein modeling, and heterogeneous catalysis, and render such scorpionate applications amenable to combinatorial methods.

A simple route to single-scorpionate nickel(II) complexes with minimum steric requirements.

Single-scorpionates of nickel(II), Tp(R)NiX or Tpm(R)NiX, are kinetic products whose preparation has generally required considerable steric constraints on the ligands (i.e., R = phenyl, tert-butyl, or isopropyl) to prevent formation of intractable two-ligand products like (Tp(R))(2)Ni. It is well established that the facial tridentate chelates hydrotris(3,5-dimethylpyrazolyl)borate (Tp*(-)), tris(3,5-dimethylpyrazolyl)methane (Tpm*), and trispyrazolylmethane (Tpm), all readily form two-ligand complexes as thermodynamic products. For the first time we report a route to the single-ligand complex TpmNiX(2)(OH(2))(n) (X = Cl and Br). We also report a novel method for making single-ligand nickel(II) scorpionate complexes using preformed tetrahalonickelate(II) ion in nitromethane. The complex Tpm*NiCl(2)(OH(2))(n) was also prepared here for the first time utilizing an alternative method first reported by Zargarian and co-workers (Inorg. Chim. Acta 2006, 2592). TpmNiX(2)(OH(2))(n) are kinetic products, and although they are stable indefinitely in the solid state, they readily convert to the thermodynamic product (Tpm)(2)Ni(2+) in solution over the course of several hours at room temperature and in a matter of minutes at 100 degrees C. The new nitromethane/NiX(4)(2-) method offers an alternative route to monoscorpionates of first row transition metals, for which tetrahalometallate ions are common. HOCH(2)Tpm (2,2,2-tris(pyrazolyl)ethanol) was covalently attached to polystyrene synthesis beads and found to bind nickel(II) (from NiX(4)(2-)) in a manner similar to Tpm. Solid state electronic spectra of supported-TpmNiCl(2) are comparable to those measured for their homogeneous complexes. Covalently supported scorpionates are expected to further extend the utility of this rich ligand class in areas of heterogeneous catalysis and metal-protein interactions.

Catalytic dioxygen activation by (nitro)(meso-tetrakis(2-n-methylpyridyl)porphyrinato)cobalt(III) cation derivatives electrostatically immobilized in nafion films: an experimental and DFT investigation.

Complexes of the (nitro)( meso-tetrakis(2- N-methylpyridyl)porphyinato)cobalt(III) cation, [LCoTMpyP(2)(NO 2)] (4+), in which L = water or ethanol have been immobilized through ionic attraction within Nafion films (Naf). These immobilized six-coordinate species, [LCoTMPyP(2)(NO 2)/Naf], have been found to catalyze the oxidation of triphenylphosphine in ethanol solution by dioxygen, therefore retaining the capacity to activate dioxygen catalytically without an additional reducing agent as was previously observed in nonaqueous solution for the non-ionic (nitro)cobalt porphyrin analogs. Heating these immobilized six-coordinate species under vacuum conditions results in the formation of the five-coordinate nitro derivatives, [CoTMPyP(2)(NO 2)/Naf] at 85 degrees C and [CoTMPyP(2)/Naf] at 110 degrees C. The catalytic oxidation of gas-phase cyclohexene with O 2 is supported only by the resulting immobilized five-coordinate nitro complex as was previously seen with the corresponding solution-phase catalyst in dichloromethane solution. The simultaneous catalytic oxidation of triphenylphosphine and cyclohexene with O 2 in the presence of the Nafion-bound six-coordinate ethanol nitro complex is also observed; however, this process is not seen for the CoTPP derivative in dichloromethane solution. The oxidation reactions do not occur with unmodified Nafion film or with Nafion-supported [BrCo(III)TmpyP]/Naf or [Co(II)TmpyP]/Naf, indicating the necessity for the nitro/nitrosyl ligand in the oxidation mechanism. The existence of a second reactive intermediate is indicated because the two simultaneous oxidation reactions depend on two distinct oxygen atom-transfer steps having different reactivity. The absence of homogeneous cyclohexene oxidation by the six-coordinate (H 2O)CoTPP(NO 2) derivatives in the presence of Ph 3P and O 2 in dichloromethane solution indicates that the second reactive intermediate is lost by an unidentified route only in solution, implying that the immobilization of it in Nafion allows it to react with cyclohexene. Although direct observation of this species has not been achieved, a comparitive DFT study of likely intermediates in several catalytic oxidation mechanisms at the BP 6-31G* level supports the possibility that this intermediate is a peroxynitro species on the basis of relative thermodynamic accessibility. The alternate intermediates evaluated include the reduced cobalt(II) porphyrin, the dioxygen adduct cobalt(III)-O 2 (-), the oxidized cobalt(II) pi-cation radical, and the nitrito complex, cobalt(III)-ONO.

Nickel-cysteine binding supported by phosphine chelates.

The effect of chelating phosphines was tested on the structure and pH-dependent stability of nickel-cysteine binding. (1,2-Bis(diphenylphosphino)ethane (dppe) and 1,1,1-tris[(diphenylphosphino)methyl]ethane (triphos) were used with three different cysteine derivatives (L-cysteine, Cys; L-cysteine ethyl ester, CysEt; cystamine, CysAm) to prepare complexes of the form (dppe)NiCysR(n+) and (triphos)NiCysR(n+) (n = 0 for Cys; n = 1 for CysEt and CysAm). Similar 31P {1H} NMR spectra for all (dppe)NiCysRn+ confirmed their square-planar P2NiSN coordination spheres. The structure of [(dppe)NiCysAm]PF6 was also confirmed by single-crystal X-ray diffraction methods. The (triphos)NiCysAm+ and (triphos)NiCysEt+ complexes were fluxional at room temperature by 31P NMR. Upon cooling to -80 degrees C, all gave spectra consistent with a P2NiSN coordination sphere with the third phosphorus uncoordinated. Temperature-dependent 31P NMR spectra showed that a trans P-Ni-S pi interaction controlled the scrambling of the coordinated triphos. In aqueous media, (dppe)NiCys was protonated at pH approximately 4-5, leading to possible formation of a nickel-cysteinethiol and eventual cysteine loss at pH < 3. The importance of N-terminus cysteine in such complexes was demonstrated by preparing (dppe)NiCys-bead and trigonal-bipyramidal Tp*NiCys-bead complexes, where Cys-bead represents cysteine anchored to polystyrene synthesis beads and Tp*- = hydrotris(3,5-dimethylpyrazolyl)borate. Importantly, results with these heterogeneous systems demonstrated the selectivity of these nickel centers for cysteine over methionine and serine and most specifically for N-terminus cysteine. The role of Ni-S pi bonding in nickel-cysteine geometries will be discussed, including how these results suggest a mechanism for the movement of electron density from nickel onto the backbone of coordinated cysteine.

Electronic structure of four-coordinate C3v nickel(II) scorpionate complexes: investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies.

A series of complexes of formula TpNiX, where Tp*- = hydrotris(3,5-dimethylpyrazole)borate and X = Cl, Br, I, has been characterized by electronic absorption spectroscopy in the visible and near-infrared (NIR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy. The crystal structure of TpNiCl has been previously reported; that for TpNiBr is given here: space group = Pmc2(1), a = 13.209(2) A, b = 8.082(2) A, c = 17.639(4) A, alpha = beta = gamma = 90 degrees , Z = 4. TpNiX contains a four-coordinate nickel(II) ion (3d8) with approximate C3v point group symmetry about the metal and a resulting S = 1 high-spin ground state. As a consequence of sizable zero-field splitting (zfs), TpNiX complexes are "EPR silent" with use of conventional EPR; however, HFEPR allows observation of multiple transitions. Analysis of the resonance field versus the frequency dependence of these transitions allows extraction of the full set of spin Hamiltonian parameters. The axial zfs parameter for TpNiX displays pronounced halogen contributions down the series: D = +3.93(2), -11.43(3), -22.81(1) cm(-1), for X = Cl, Br, I, respectively. The magnitude and change in sign of D observed for TpNiX reflects the increasing bromine and iodine spin-orbit contributions facilitated by strong covalent interactions with nickel(II). These spin Hamiltonian parameters are combined with estimates of 3d energy levels based on the visible-NIR spectra to yield ligand-field parameters for these complexes following the angular overlap model (AOM). This description of electronic structure and bonding in a pseudotetrahedral nickel(II) complex can enhance the understanding of similar sites in metalloproteins, both native nickel enzymes and nickel-substituted zinc enzymes.

Ligand redox effects in the synthesis, electronic structure, and reactivity of an alkyl-alkyl cross-coupling catalyst.

The ability of the terpyridine ligand to stabilize alkyl complexes of nickel has been central in obtaining a fundamental understanding of the key processes involved in alkyl-alkyl cross-coupling reactions. Here, mechanistic studies using isotopically labeled (TMEDA)NiMe(2) (TMEDA = N,N,N',N'-tetramethylethylenediamine) have shown that an important catalyst in alkyl-alkyl cross-coupling reactions, (tpy')NiMe (2b, tpy' = 4,4',4' '-tri-tert-butylterpyridine), is not produced via a mechanism that involves the formation of methyl radicals. Instead, it is proposed that (terpyridine)NiMe complexes arise via a comproportionation reaction between a Ni(II)-dimethyl species and a Ni(0) fragment in solution upon addition of a terpyridine ligand to (TMEDA)NiMe(2). EPR and DFT studies on the paramagnetic (terpyridine)NiMe (2a) both suggest that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand. Thus, an important consequence of these results is that alkyl halide reduction by (terpyridine)NiR(alkyl) complexes appears to be substantially ligand based. A comprehensive survey investigating the catalytic reactivity of related ligand derivatives suggests that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors.

A stable monomeric nickel borohydride.

A stable discrete nickel borohydride complex (Tp*NiBH(4) or Tp*NiBD(4)) was prepared using the nitrogen-donor ligand hydrotris(3,5-dimethylpyrazolyl)borate (Tp*-). This complex represents one of the best characterized nickel(II) borohydrides to date. Tp*NiBH(4) and Tp*NiBD(4) are stable toward air, boiling water, and high temperatures (mp > 230 degrees C dec). X-ray crystallographic measurements for Tp*NiBH(4) showed a six-coordinate geometry for the complex, with the nickel(II) center facially coordinated by three bridging hydrogen atoms from borohydride and a tridentate Tp(-) ligand. For Tp*NiBH(4), the empirical formula is C(15)H(26)B(2)N(6)Ni, a = 13.469(9) A, b = 7.740(1) A, c = 18.851(2) A, beta = 107.605(9) degrees, the space group is monoclinic P2(1)/c, and Z = 4. Infrared measurements confirmed the presence of bridging hydrogen atoms; both nu(B[bond]H)(terminal) and nu(B[bond]H)(bridging) are assignable and shifted relative to nu(B-D) of Tp*NiBD(4) by amounts in agreement with theory. Despite their hydrolytic stability, Tp*NiBH(4) and Tp*NiBD(4) readily reduce halocarbon substrates, leading to the complete series of Tp*NiX complexes (X = Cl, Br, I). These reactions showed a pronounced hydrogen/deuterium rate dependence (k(H)/k(D) approximately 3) and sharp isosbestic points in progressive electronic spectra. Nickel K-edge X-ray absorption spectroscopy (XAS) measurements of a hydride-rich nickel center were obtained for Tp*NiBH(4), Tp*NiBD(4), and Tp*NiCl. X-ray absorption near-edge spectroscopy results confirmed the similar six-coordinate geometries for Tp*NiBH(4) and Tp*NiBD(4). These contrasted with XAS results for the crystallographically characterized pseudotetrahedral Tp*NiCl complex. The stability of Tp*Ni-coordinated borohydride is significant given this ion's accelerated decomposition and hydrolysis in the presence of transition metals and simple metal salts.