The Active-Site [4Fe-4S] Cluster in the Isoprenoid Biosynthesis Enzyme IspH Adopts Unexpected Redox States during Ligand Binding and Catalysis.

(E)-4-Hydroxy-3-methylbut-2-enyl diphosphate reductase, or IspH (formerly known as LytB), catalyzes the terminal step of the bacterial methylerythritol phosphate (MEP) pathway for isoprene synthesis. This step converts (E)-4-hydroxy-3-methylbut-2-enyl diphosphate (HMBPP) into one of two possible isomeric products, either isopentenyl diphosphate (IPP) or dimethylallyl diphosphate (DMAPP). This reaction involves the removal of the C4 hydroxyl group of HMBPP and addition of two electrons. IspH contains a [4Fe-4S] cluster in its active site, and multiple cluster-based paramagnetic species of uncertain redox and ligation states can be detected after incubation with reductant, addition of a ligand, or during catalysis. To characterize the clusters in these species, 57Fe-labeled samples of IspH were prepared and studied by electron paramagnetic resonance (EPR), 57Fe electron-nuclear double resonance (ENDOR), and Mössbauer spectroscopies. Notably, this ENDOR study provides a rarely reported, complete determination of the 57Fe hyperfine tensors for all four Fe ions in a [4Fe-4S] cluster. The resting state of the enzyme (Ox) has a diamagnetic [4Fe-4S]2+ cluster. Reduction generates [4Fe-4S]+ (Red) with both S = 1/2 and S = 3/2 spin ground states. When the reduced enzyme is incubated with substrate, a transient paramagnetic reaction intermediate is detected (Int) which is thought to contain a cluster-bound substrate-derived species. The EPR properties of Int are indicative of a 3+ iron-sulfur cluster oxidation state, and the Mössbauer spectra presented here confirm this. Incubation of reduced enzyme with the product IPP induced yet another paramagnetic [4Fe-4S]+ species (Red+P) with S = 1/2. However, the g-tensor of this state is commonly associated with a 3+ oxidation state, while Mössbauer parameters show features typical for 2+ clusters. Implications of these complicated results are discussed.

Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene.

We introduce the arsenido ligand onto the TiIV ion, yielding a remarkably covalent Ti≡As bond and the parent arsinidene Ti═AsH moiety. An anionic arsenido ligand is assembled via reductive decarbonylation involving the discrete TiII salt [K(cryptand)][(PN)2TiCl] (1) (cryptand = 222-Kryptofix) and Na(OCAs)(dioxane)1.5 in thf/toluene to produce the mixed alkali ate-complex [(PN)2Ti(As)]2(µ2-KNa(thf)2) (2) and the discrete salt [K(cryptand)][(PN)2Ti≡As] (3) featuring a terminal Ti≡As ligand. Protonation of 2 or 3 with various weak acids cleanly forms the parent arsinidene [(PN)2Ti═AsH] (4), which upon deprotonation with KCH2Ph in thf generates the more symmetric anionic arsenido [(PN)2Ti(As){µ2-K(thf)2}]2 (5). Experimental and computational studies suggest the pKa of 4 to be ∼23, and the bond orders in 2, 3, and 5 are all in the range of a Ti≡As triple bond, with decreasing bond order in 4.

Electronic Structure of Three-Coordinate FeII and CoII ß-Diketiminate Complexes.

The ß-diketiminate supporting group, [ArNCRCHCRNAr]-, stabilizes low coordination number complexes. Four such complexes, where R = tert-butyl, Ar = 2,6-diisopropylphenyl, are studied: (nacnactBu)ML, where M = FeII, CoII and L = Cl, CH3. These are denoted FeCl, FeCH3, CoCl, and CoCH3 and have been previously reported and structurally characterized. The two FeII complexes (S = 2) have also been previously characterized by Mössbauer spectroscopy, but only indirect assessment of the ligand-field splitting and zero-field splitting (zfs) parameters was available. Here, EPR spectroscopy is used, both conventional field-domain for the CoII complexes (with S = 3/2) and frequency-domain, far-infrared magnetic resonance spectroscopy (FIRMS) for all four complexes. The CoII complexes were also studied by magnetometry. These studies allow accurate determination of the zfs parameters. The two FeII complexes are similar with nearly axial zfs and large magnitude zfs given by D = -37 ± 1 cm-1 for both. The two CoII complexes likewise exhibit large and nearly axial zfs, but surprisingly, CoCl has positive D = +55 cm-1 while CoCH3 has negative D = -49 cm-1. Theoretical methods were used to probe the electronic structures of the four complexes, which explain the experimental spectra and the zfs parameters.

Ynamide and Azaalleneyl. Acid-Base Promoted Chelotropic and Spin-State Rearrangements in a Versatile Heterocumulene [(Ad)NCC(tBu)].

We introduce the heterocumulene ligand [(Ad)NCC(tBu)]- (Ad=1-adamantyl (C10H15), tBu=tert-butyl, (C4H9)), which can adopt two forms, the azaalleneyl and ynamide. This ligand platform can undergo a reversible chelotropic shift using Brønsted acid-base chemistry, which promotes an unprecedented spin-state change of the [VIII] ion. These unique scaffolds are prepared via addition of 1-adamantyl isonitrile (C≡NAd) across the alkylidyne in complexes [(BDI)V≡CtBu(OTf)] (A) (BDI-=ArNC(CH3)CHC(CH3)NAr), Ar=2,6-iPr2C6H3) and [(dBDI)V≡CtBu(OEt2)] (B) (dBDI2-=ArNC(CH3)CHC(CH2)NAr). Complex A reacts with C≡NAd, to generate the high-spin [VIII] complex with a κ1-N-ynamide ligand, [(BDI)V{κ1-N-(Ad)NCC(tBu)}(OTf)] (1). Conversely, B reacts with C≡NAd to generate a low-spin [VIII] diamagnetic complex having a chelated κ2-C,N-azaalleneyl ligand, [(dBDI)V{κ2-N,C-(Ad)NCC(tBu)}] (2). Theoretical studies have been applied to better understand the mechanism of formation of 2 and the electronic reconfiguration upon structural rearrangement by the alteration of ligand denticity between 1 and 2.

Metallacyclobuta-(2,3)-diene: A Bidentate Ligand for Stream-line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene.

Described here is a direct entry to two examples of 3d transition metal catalysts that are active for the cyclic polymerization of phenylacetylene, namely, [(BDI)M{κ2 -C,C-(Me3 SiC3 SiMe3 )}] (2-M) (BDI=[ArNC(CH3 )]2 CH- , Ar=2,6-i Pr2 C6 H3 ; M=Ti, V). Catalysts are prepared in one step by the treatment of [(BDI)MCl2 ] (1-M, M=Ti, V) with 1,3-dilithioallene [Li2 (Me3 SiC3 SiMe3 )]. Complexes 2-M have been spectroscopically and structurally characterized and the polymers that are catalytically formed from phenylacetylene were verified to have a cyclic topology based on a combination of size-exclusion chromatography (SEC) and intrinsic viscosity studies. Two-electron oxidation of 2-V with nitrous oxide (N2 O) cleanly yields a [VV ] alkylidene-alkynyl oxo complex [(BDI)V(=O){κ1 -C-(=C(SiMe3 )CC(SiMe3 ))}] (3), which lends support for how this scaffold in 2-M might be operating in the polymerization of the terminal alkyne. This work demonstrates how alkylidynes can be circumvented using 1,3-dianionic allene as a segue into M-C multiple bonds.

Divalent Titanium via Reductive N-C Coupling of a TiIV Nitrido with π-Acids.

The nitrido-ate complex [(PN)2Ti(N){µ2-K(OEt2)}]2 (1) (PN-=(N-(2-PiPr2-4-methylphenyl)-2,4,6-Me3C6H2) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five-coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=NtBu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene, [(PN)2Ti(NCE)] (E=O, (6); E=NAd (7), NtBu (8)) and characterization by CW X-band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e- reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high-frequency and -field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C6F5)4] resulted in a ligand disproportionated TiIV complex having transoid carbodiimides, [(PN)2Ti(NCNAd)2] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as TiII→TiIII→TiIV and increasing order of π-donation as TiII→TiIII→TiIV, thus displaying more covalency in TiIII species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N-atom to CO and CNAd.

Spectroscopic and Magnetic Studies of Co(II) Scorpionate Complexes: Is There a Halide Effect on Magnetic Anisotropy?

The observation of single-molecule magnetism in transition-metal complexes relies on the phenomenon of zero-field splitting (ZFS), which arises from the interplay of spin-orbit coupling (SOC) with ligand-field-induced symmetry lowering. Previous studies have demonstrated that the magnitude of ZFS in complexes with 3d metal ions is sometimes enhanced through coordination with heavy halide ligands (Br and I) that possess large free-atom SOC constants. In this study, we systematically probe this "heavy-atom effect" in high-spin cobalt(II)-halide complexes supported by substituted hydrotris(pyrazol-1-yl)borate ligands (TptBu,Me and TpPh,Me). Two series of complexes were prepared: [CoIIX(TptBu,Me)] (1-X; X = F, Cl, Br, and I) and [CoIIX(TpPh,Me)(HpzPh,Me)] (2-X; X = Cl, Br, and I), where HpzPh,Me is a monodentate pyrazole ligand. Examination with dc magnetometry, high-frequency and -field electron paramagnetic resonance, and far-infrared magnetic spectroscopy yielded axial (D) and rhombic (E) ZFS parameters for each complex. With the exception of 1-F, complexes in the four-coordinate 1-X series exhibit positive D-values between 10 and 13 cm-1, with no dependence on halide size. The five-coordinate 2-X series exhibit large and negative D-values between -60 and -90 cm-1. Interpretation of the magnetic parameters with the aid of ligand-field theory and ab initio calculations elucidated the roles of molecular geometry, ligand-field effects, and metal-ligand covalency in controlling the magnitude of ZFS in cobalt-halide complexes.

Cooperative Activation of CO2 and Epoxide by a Heterobinuclear Al-Fe Complex via Radical Pair Mechanisms.

Activation of inert molecules like CO2 is often mediated by cooperative chemistry between two reactive sites within a catalytic assembly, the most common form of which is Lewis acid/base bifunctionality observed in both natural metalloenzymes and synthetic systems. Here, we disclose a heterobinuclear complex with an Al-Fe bond that instead activates CO2 and other substrates through cooperative behavior of two radical intermediates. The complex Ldipp(Me)AlFp (2, Ldipp = HC{(CMe)(2,6-iPr2C6H3N)}2, Fp = FeCp(CO)2, Cp = η5-C5H5) was found to insert CO2 and cyclohexene oxide, producing LdippAl(Me)(µ:κ2-O2C)Fp (3) and LdippAl(Me)(µ-OC6H10)Fp (4), respectively. Detailed mechanistic studies indicate unusual pathways in which (i) the Al-Fe bond dissociates homolytically to generate formally AlII and FeI metalloradicals, then (ii) the metalloradicals add to substrate in a pairwise fashion initiated by O-coordination to Al. The accessibility of this unusual mechanism is aided, in part, by the redox noninnocent nature of Ldipp that stabilizes the formally AlII intermediates, instead giving them predominantly AlIII-like physical character. The redox noninnocent nature of the radical intermediates was elucidated through direct observation of LdippAl(Me)(OCPh2) (22), a metalloradical species generated by addition of benzophenone to 2. Complex 22 was characterized by X-band EPR, Q-band EPR, and ENDOR spectroscopies as well as computational modeling. The "radical pair" pathway represents an unprecedented mechanism for CO2 activation.

Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4 Double-Diamond Core.

Transmetallation of [VCl3(THF)3] and [TlTptBu,Me] afforded [(TptBu,Me)VCl2] (1, TptBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC8 to form a C3v symmetric VII complex, [(TptBu,Me)VCl] (2). Complex 1 has a high-spin (S = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an S = 3/2 4A2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN3 to form the VV nitride-azide complex [(TptBu,Me)V≡N(N3)] (3). A likely VIII azide intermediate en route to 3, [(TptBu,Me)VCl(N3)] (4), was isolated by reacting 1 with N3SiMe3. Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(TptBu,Me)V(N3)2] (A), leading to 3. Reduction of 3 with KC8 furnishes a trinuclear and mixed-valent nitride, [{(TptBu,Me)V}2(µ4-VN4)] (5), conforming to a Robin-Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN3 to produce an azide-bridged dimer, [{(TptBu,Me)V}2(1,3-µ2-N3)2] (6), with two antiferromagnetically coupled high-spin VII ions. Complex 5 could be independently produced along with [(κ2-TptBu,Me)2V] upon photolysis of 6 in arene solvents. The putative {VIV≡N} intermediate, [(TptBu,Me)V≡N] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(TptBu,Me)V≡N(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [(κ2-TptBu,Me)2V]. A more stable adduct (B-OPPh3) was prepared by reacting B-THF with OPPh3. These adducts of B are the first neutral and mononuclear VIV nitride complexes to be isolated.

Linewidth, field, and frequency in electron paramagnetic resonance (EPR) spectroscopy.

EPR spectroscopy requires a combination of fixed microwave radiation and resonant external magnetic field. Bigger is not necessarily better in that low-frequency and -field EPR (LFEPR) can provide useful information as well as reduced linewidths that can allow better observation of hyperfine coupling. More importantly, LFEPR allows very low g values to be readily observed, such as often found in low-spin d5 systems.

Structural and Spectroscopic Characterization of a Zinc-Bound N-Oxyphthalimide Radical.

Thermolysis of a 1:1:1 mixture of MeLH (MeL = {(2,6-iPr2C6H3)NC(Me)}2CH), N-hydroxyphthalimide (HOPth), and diethylzinc in toluene at 77 °C provided [MeLZn(OPth)] (1) in good yield after workup. The subsequent reduction of 1 with 1.3 equiv of KC8 and 1 equiv of 2.2.2-cryptand, in tetrahydrofuran, provided [K(2.2.2-cryptand)][MeLZn(OPth)] (2) in 74% yield after workup. Characterization of 2 via X-ray crystallography and electron paramagnetic resonance spectroscopy reveals the presence of an S = 1/2 radical on the N-oxyphthalimide ligand. Importantly, these data represent the first structural and spectroscopic confirmation of the redox activity of a metal-bound N-oxyphthalimide fragment, expanding the range of structurally characterized redox-active ligands.

The Ruthenium Nitrosyl Moiety in Clusters: Trinuclear Linear µ-Hydroxido Magnesium(II)-Diruthenium(II), µ3-Oxido Trinuclear Diiron(III)-Ruthenium(II), and Tetranuclear µ4-Oxido Trigallium(III)-Ruthenium(II) Complexes.

The ruthenium nitrosyl moiety, {RuNO}6, is important as a potential releasing agent of nitric oxide and is of inherent interest in coordination chemistry. Typically, {RuNO}6 is found in mononuclear complexes. Herein we describe the synthesis and characterization of several multimetal cluster complexes that contain this unit. Specifically, the heterotrinuclear µ3-oxido clusters [Fe2RuCl4(µ3-O)(µ-OMe)(µ-pz)2(NO)(Hpz)2] (6) and [Fe2RuCl3(µ3-O)(µ-OMe)(µ-pz)3(MeOH)(NO)(Hpz)][Fe2RuCl3(µ3-O)(µ-OMe)(µ-pz)3(DMF)(NO)(Hpz)] (7·MeOH·2H2O) and the heterotetranuclear µ4-oxido complex [Ga3RuCl3(µ4-O)(µ-OMe)3(µ-pz)4(NO)] (8) were prepared from trans-[Ru(OH)(NO)(Hpz)4]Cl2 (5), which itself was prepared via acidic hydrolysis of the linear heterotrinuclear complex {[Ru(µ-OH)(µ-pz)2(pz)(NO)(Hpz)]2Mg} (4). Complex 4 was synthesized from the mononuclear Ru complexes (H2pz)[trans-RuCl4(Hpz)2] (1), trans-[RuCl2(Hpz)4]Cl (2), and trans-[RuCl2(Hpz)4] (3). The new compounds 4-8 were all characterized by elemental analysis, ESI mass spectrometry, IR, UV-vis, and 1H NMR spectroscopy, and single-crystal X-ray diffraction, with complexes 6 and 7 being characterized also by temperature-dependent magnetic susceptibility measurements and Mössbauer spectroscopy. Magnetometry indicated a strong antiferromagnetic interaction between paramagnetic centers in 6 and 7. The ability of 4 and 6-8 to form linkage isomers and release NO upon irradiation in the solid state was investigated by IR spectroscopy. A theoretical investigation of the electronic structure of 6 by DFT and ab initio CASSCF/NEVPT2 calculations indicated a redox-noninnocent behavior of the NO ancillary ligand in 6, which was also manifested in TD-DFT calculations of its electronic absorption spectrum. The electronic structure of 6 was also studied by an X-ray charge density analysis.

Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile- versus Proton-Coupled Electron Transfer.

Nitride complexes are key species in homogeneous nitrogen fixation to NH3 via stepwise proton-coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N2 -derived nitrides requires new strategies to enable efficient reductive nitride transfer in the presence of organic electrophiles. We here present a 2-step protocol for the conversion of dinitrogen to benzonitrile. Photoelectrochemical, reductive N2 splitting produces a rhenium(V) nitride with unfavorable PCET thermochemistry towards ammonia generation. However, N-benzoylation stabilizes subsequent reduction as a basis for selective nitrogen transfer in the presence of the organic electrophile and Brønsted acid at mild reduction potentials. This work offers a new strategy for photoelectrosynthetic nitrogen fixation beyond ammonia-to yield nitrogenous organic products.

Applying Unconventional Spectroscopies to the Single-Molecule Magnets, Co(PPh3 )2 X2 (X=Cl, Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling.

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh3 )2 X2 (Co-X; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X, showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.

Electronic Structure of Tetrahedral, S = 2, [Fe{(EPiPr2)2N}2], E = S, Se, Complexes: Investigation by High-Frequency and -Field Electron Paramagnetic Resonance, 57Fe Mössbauer Spectroscopy, and Quantum Chemical Studies.

In this work, we assessed the electronic structures of two pseudotetrahedral complexes of FeII, [Fe{(SPiPr2)2N}2] (1) and [Fe{(SePiPr2)2N}2] (2), using high-frequency and -field EPR (HFEPR) and field-dependent 57Fe Mössbauer spectroscopies. This investigation revealed S = 2 ground states characterized by moderate, negative zero-field splitting (zfs) parameters D. The crystal-field (CF) theory analysis of the spin Hamiltonian (sH) and hyperfine structure parameters revealed that the orbital ground states of 1 and 2 have a predominant dx2-y2 character, which is admixed with dz2 (∼10%). Although replacing the S-containing ligands of 1 by their Se-containing analogues in 2 leads to a smaller |D| value, our theoretical analysis, which relied on extensive ab initio CASSCF calculations, suggests that the ligand spin-orbit coupling (SOC) plays a marginal role in determining the magnetic anisotropy of these compounds. Instead, the dx2-y2ß â†’ dxyß excitations yield a large negative contribution, which dominates the zfs of both 1 and 2, while the different energies of the dx2-y2ß â†’ dxzß transitions are the predominant factor responsible for the difference in zfs between 1 and 2. The electronic structures of these compounds are contrasted with those of other [FeS4] sites, including reduced rubredoxin by considering a D2-type distortion of the [Fe(E-X)4] cores, where E = S, Se; X = C, P. Our combined CASSCF/DFT calculations indicate that while the character of the orbital ground state and the quintet excited states' contribution to the zfs of 1 and 2 are modulated by the magnitude of the D2 distortion, this structural change does not impact the contribution of the excited triplet states.

Electronic Structure and Magnetic Properties of a Low-Spin CrII Complex: trans-[CrCl2(dmpe)2] (dmpe = 1,2-Bis(dimethylphosphino)ethane).

Octahedral coordination complexes of the general formula trans-[MX2(R2ECH2CH2ER2)2] (MII = Ti, V, Cr, Mn; E = N, P; R = alkyl, aryl) are a cornerstone of both coordination and organometallic chemistry, and many of these complexes are known to have unique electronic structures that have been incompletely examined. The trans-[CrCl2(dmpe)2] complex (dmpe = Me2PCH2CH2PMe2), originally reported by Girolami and co-workers in 1985, is a rare example of a six-coordinate d4 system with an S = 1 (spin triplet) ground state, as opposed to the high-spin (S = 2, spin quintet) state. The ground-state properties of S = 1 systems are challenging to study using conventional spectroscopic methods, and consequently, the electronic structure of trans-[CrCl2(dmpe)2] has remained largely unexplored. In this present work, we have employed high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy to characterize the ground-state electronic structure of trans-[CrCl2(dmpe)2]. This analysis yielded a complete set of spin Hamiltonian parameters for this S = 1 complex: D = +7.39(1) cm-1, E = +0.093(1) (E/D = 0.012), and g = [1.999(5), 2.00(1), 2.00(1)]. To develop a detailed electronic structure description for trans-[CrCl2(dmpe)2], we employed both classical ligand-field theory and quantum chemical theory (QCT) calculations, which considered all quintet, triplet, and singlet ligand-field states. While the high density of states suggests an unexpectedly complex electronic structure for this "simple" coordination complex, both the ligand-field and QCT methods were able to reproduce the experimental spin Hamiltonian parameters quite nicely. The QCT computations were also used as a basis for assigning the electronic absorption spectrum of trans-[CrCl2(dmpe)2] in toluene.

High-Frequency and -Field Electron Paramagnetic Resonance Spectroscopic Analysis of Metal-Ligand Covalency in a 4f7 Valence Series (Eu2+, Gd3+, and Tb4+).

The recent isolation of molecular tetravalent lanthanide complexes has enabled renewed exploration of the effect of oxidation state on the single-ion properties of the lanthanide ions. Despite the isotropic nature of the 8S ground state in a tetravalent terbium complex, [Tb(NP(1,2-bis-tBu-diamidoethane)(NEt2))4], preliminary X-band electron paramagnetic resonance (EPR) measurements on tetravalent terbium complexes show rich spectra with broad resonances. The complexity of these spectra highlights the limits of conventional X-band EPR for even qualitative determination of zero-field splitting (ZFS) in these complexes. Therefore, we report the synthesis and characterization of a novel valence series of 4f7 molecular complexes spanning three oxidation states (Eu2+, Gd3+, and Tb4+) featuring a weak-field imidophosphorane ligand system, and employ high-frequency and -field electron paramagnetic resonance (HFEPR) to obtain quantitative values for ZFS across this valence series. The series was designed to minimize deviation in the first coordination sphere from the pseudotetrahedral geometry in order to directly interrogate the role of metal identity and charge on the complexes' electronic structures. These HFEPR studies are supported by crystallographic analysis and quantum-chemical calculations to assess the relative covalent interactions in each member of this valence series and the effect of the oxidation state on the splitting of the ground state and first excited state.

Nitrene Photochemistry of Manganese N-Haloamides*.

Manganese complexes supported by macrocyclic tetrapyrrole ligands represent an important platform for nitrene transfer catalysis and have been applied to both C-H amination and olefin aziridination catalysis. The reactivity of the transient high-valent Mn nitrenoids that mediate these processes renders characterization of these species challenging. Here we report the synthesis and nitrene transfer photochemistry of a family of MnIII N-haloamide complexes. The S=2 N-haloamide complexes are characterized by 1 H NMR, UV-vis, IR, high-frequency and -field EPR (HFEPR) spectroscopies, and single-crystal X-ray diffraction. Photolysis of these complexes results in the formal transfer of a nitrene equivalent to both C-H bonds, such as the α-C-H bonds of tetrahydrofuran, and olefinic substrates, such as styrene, to afford aminated and aziridinated products, respectively. Low-temperature spectroscopy and analysis of kinetic isotope effects for C-H amination indicate halogen-dependent photoreactivity: Photolysis of N-chloroamides proceeds via initial cleavage of the Mn-N bond to generate MnII and amidyl radical intermediates; in contrast, photolysis of N-iodoamides proceeds via N-I cleavage to generate a MnIV nitrenoid (i.e., {MnNR}7 species). These results establish N-haloamide ligands as viable precursors in the photosynthesis of metal nitrenes and highlight the power of ligand design to provide access to reactive intermediates in group-transfer catalysis.

Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture.

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (≈550 cm-1 ) of the intermediate-spin S=3/2 excited states to the high-spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin-admixture model evidences a sizable contribution (≈15 %) of S=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm-1 ). Frequency-domain EPR spectroscopy allowed the mS = |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero-field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field-domain EPR studies are consistent with this model, which is also supported by theoretical calculations.

Redox-Controlled Reactivity at Boron: Parallels to Frustrated Lewis/Radical Pair Chemistry.

We report the synthesis of new Lewis-acidic boranes tethered to redox-active vanadium centers, (Ph2N)3V(µ-N)B(C6F5)2 (1a) and (N(CH2CH2N(C6F5))3)V(µ-N)B(C6F5)2 (1b). Redox control of the VIV/V couple resulted in switchable borane versus "hidden" boron radical reactivity, mimicking frustrated Lewis versus frustrated radical pair (FLP/FRP) chemistry, respectively. Whereas heterolytic FLP-type addition reactions were observed with the VV complex (1b) in the presence of a bulky phosphine, homolytic peroxide, or Sn-hydride bond cleavage reactions were observed with the VIV complex, [CoCp2*][(N(CH2CH2N(C6F5))3)V(µ-N)B(C6F5)2] (3b), indicative of boron radical anion character. The extent of radical character was probed by spectroscopic and computational means. Together, these results demonstrate that control of the VIV/V oxidation states allows these compounds to access reactivity observed in both FLP and FRP chemistry.