Stephen Sproules

Electronic Structure of the [Tris(dithiolene)chromium]z(z=0,1―, 2―, 3―) Electron Transfer Series and Their Manganese(IV) Analogues. An X-ray Absorption Spectroscopic and Density Functional Theoretical Study

From the reaction mixture of 3,6-dichlorobenzene-1,2-dithiol, H(2)(Cl(2)-bdt), [CrCl(3)(thf)(3)], and NEt(3) in tetrahydrofuran (thf) in the presence of air, dark green crystals of [N(n-Bu)(4)](2)[Cr(Cl(2)-bdt)(3)] (S = 1) (1) were isolated upon addition of [N(n-Bu)(4)]Br. Oxidation of the AsPh(4)(+) salt of 1 with [Fc]PF(6) yielded microcrystals of [AsPh(4)][Cr(Cl(2)-bdt)(3)] (S = (1)/(2)) (2) whereas the reduction of 1 with sodium amalgam produced light green crystals of [N-(n-Bu)(4)](3)[Cr(Cl(2)-bdt)(3)].thf (S = (3)/(2)) (3). The corresponding maleonitriledithiolato complexes [PPh(4)](2)[Cr(mnt)(3)] (S = 1) (4) and [PPh(4)](3)[Cr(mnt)(3)] (S = (3)/(2)) (5) have been synthesized. Isoelectronic manganese complexes of 3 and 5, namely, [NEt(4)](2)[Mn(Cl(2)-bdt)(3)] (S = (3)/(2)) (6) and [PPh(4)](2)[Mn(mnt)(3)] (S = (3)/(2)) (7), have also been prepared. Complexes 1, 6, and 7 have been characterized by single crystal X-ray crystallography. Complexes 1-7 have been electrochemically studied and their UV-vis and electron paramagnetic resonance spectra (EPR) have been recorded; magnetic properties have been elucidated by temperature-dependent susceptibility measurements. It is shown by chromium K-edge and sulfur K-edge X-ray absorption spectroscopy (XAS) that the oxidation state of the central Cr ion in each compound is the same (+III, d(3)) and that all one-electron redox processes are ligand-based, involving one, two, or three ligand pi radical monoanions. Complexes 6 and 7 possess a Mn(IV) ion with three dianionic ligands. The results have been corroborated by broken symmetry (BS) density functional theoretical (DFT) calculations by using the B3LYP functional. Time-dependent DFT calculations have been performed to calculate the metal and sulfur K-pre-edges. It is suggested that the neutral complexes [Cr(dithiolene)(3)](0) S = 0 possess octahedral rather than trigonal prismatic CrS(6) polyhedra. Three ligand pi radicals (S(rad) = (1)/(2)) couple antiferromagnetically to the central Cr(III) ion (d(3)) yielding the observed diamagnetic ground state. It is established that the four members of the [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-) electron transfer series are related by ligand-based one-electron transfer processes; for each of the four members it is shown that they contain a central Cr(III) (d(3)) ion, and the CrS(6) polyhedron is a (distorted) octahedron.

Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine-Boranes

Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me(2) NH⋅BH(3). Such Ti(III) -amidoborane complexes are generated in [Cp(2)Ti]-catalyzed amine-borane dehydrocoupling reactions, for which diamagnetic M(II) and M(IV) species have been previously postulated as precatalysts and intermediates.

A Step beyond the Feltham–Enemark Notation: Spectroscopic and Correlated ab Initio Computational Support for an Antiferromagnetically Coupled M(II)–(NO)− Description of Tp*M(NO) (M = Co, Ni)

Multiple spectroscopic and computational methods were used to characterize the ground-state electronic structure of the novel {CoNO}(9) species Tp*Co(NO) (Tp* = hydro-tris(3,5-Me(2)-pyrazolyl)borate). The metric parameters about the metal center and the pre-edge region of the Co K-edge X-ray absorption spectrum were reproduced by density functional theory (DFT), providing a qualitative description of the Co-NO bonding interaction as a Co(II) (S(Co) = 3/2) metal center, antiferromagnetically coupled to a triplet NO(-) anion (S(NO) = 1), an interpretation of the electronic structure that was validated by ab initio multireference methods (CASSCF/MRCI). Electron paramagnetic resonance (EPR) spectroscopy revealed significant g-anisotropy in the S = ½ ground state, but the linear-response DFT performed poorly at calculating the g-values. Instead, CASSCF/MRCI computational studies in conjunction with quasi-degenerate perturbation theory with respect to spin-orbit coupling were required for obtaining accurate modeling of the molecular g-tensor. The computational portion of this work was extended to the diamagnetic Ni analogue of the Co complex, Tp*Ni(NO), which was found to consist of a Ni(II) (S(Ni) = 1) metal center antiferromagnetically coupled to an S(NO) = 1 NO(-). The similarity between the Co and Ni complexes contrasts with the previously studied Cu analogues, for which a Cu(I) bound to NO(0) formulation has been described. This discrepancy will be discussed along with a comparison of the DFT and ab initio computational methods for their ability to predict various spectroscopic and molecular features.

Monoanionic molybdenum and tungsten tris(dithiolene) complexes: a multifrequency EPR study.

Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-•))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-•))](1-) ↔ [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-•))](1-) complexes highlights tungstens preference for higher oxidation states.

(α-Diimine)chromium complexes: molecular and electronic structures; a combined experimental and density functional theoretical study

Dark brown crystals of [Cr( (1)L) 2] ( 1) were obtained from the reaction of [Cr (III)(acac) 3] (acac (-) = 2,4-pentanedionate) with 2 equiv of 2-methyl-1,4-bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene ( (1)L) and 3 equiv of sodium in tetrahydrofuran (thf) under an Ar atmosphere. Complex 1 possesses an S = 1 ground state, which is attained via intramolecular antiferromagnetic coupling between a high-spin Cr (II) ion ( S Cr = 2) and two anionic alpha-diiminato(1-) ligand pi radicals ( (1)L (*)) (1-). The molecular structure of 1 exhibits a distorted tetrahedral, nearly square-planar geometry. The average C-N imine bond length at 1.346 A is characteristic for the pi radical anion ( (1)L (*)) (1-), and therefore, the electronic structure of 1 is best described as [Cr (II)( (1)L (*)) 2]. This has been confirmed by broken symmetry density functional theoretical calculations BS(4,2) (DFT) at the B3LYP level. The reaction of [Cr (III)(acac) 3] with 1 equiv of 2,3-dimethyl-1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene ( (2)L) and 1 equiv of Na in thf under Ar yields red-brown crystals of [Cr (III)( (2)L (*))(acac) 2] ( 2) ( S = 1). The oxidation of 2 with 1 equiv of Fc(PF 6) (Fc (+) = ferrocenium) in CH 2Cl 2 affords crystals of [Cr (III)( (2)L (ox))(acac) 2](PF 6) ( 3) ( S = (3)/ 2). The crystal structure determinations of 2 and 3 revealed that 2 contains a neutral, octahedral Cr (III) species [Cr (III)( (2)L (*))(acac) 2], whereas in 3 the ligand is oxidized, yielding an octahedral monocation [Cr (III)( (2)L (ox))(acac) 2] (+). These electronic structures have been confirmed by DFT calculations.

Six-Membered Electron Transfer Series [V(dithiolene)3]z (z=1+, 0, 1-, 2-, 3―, 4―). An X-ray Absorption Spectroscopic and Density Functional Theoretical Study

The electronic structures of vanadium centers coordinated by three dithiolene ligands have been elucidated by using a host of physical methods: X-ray crystallography, cyclic voltammetry, electronic absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies, augmented by density functional theoretical (DFT) calculations. The consensus electronic structure derived from this approach is a V(IV) central ion for the neutral, monoanionic, and dianionic members of this electron transfer series, where the tris(dithiolene) ligand units are (L(3))(4-), (L(3))(5-*), and (L(3))(6-), respectively. The trigonal prismatic monoanions, [V(IV)(L(3)(5-*))](1-) (S = 0), are defined as singlet diradicals where the crystallographically observed dithiolene fold results from strong antiferromagnetic coupling between the metal- and ligand-based magnetic orbitals. These results are contrasted with the corresponding tris(dioxolene)vanadium electron transfer series toward establishing the factors that govern the molecular trigonal prismatic or octahedral geometries in systems with three redox noninnocent ligands.

Characterization and electronic structures of five members of the electron transfer series [Re(benzene-1,2-dithiolato)3](z) (z = 1+, 0, 1-, 2-, 3-): a spectroscopic and density functional theoretical study.

The reaction of ReCl(5) with 3 equiv of a benzene-1,2-dithiolate derivative in CH(3)CN produced, after the addition of [C(8)H(16)N]Br ([C(8)H(16)N](+) is 5-azonia-spiro[4,4]nonane), brownish-green crystals of [C(8)H(16)N][Re(tms)(3)] (1c) and [C(8)H(16)N][Re(Cl(2)-bdt)(3)] (2c), where (tms)(2-) represents 3,6-bis(trimethylsilyl)benzene-1,2-dithiolate and (Cl(2)-bdt)(2-) is 3,6-dichlorobenzene-1,2-dithiolate. Chemical reduction of [Re(bdt)(3)] (3b) with n-butyllithium in the presence of PPh(4)Br yielded [PPh(4)][Re(bdt)(3)] (3c), where (bdt)(2-) is benzene-1,2-dithiolate. The three monoanionic complexes possess a diamagnetic ground state (Re(V), d(2), S = 0). The crystal structures of 1c x 2 CH(3)CN and 2c x C(3)H(6)O have been determined by X-ray crystallography. The electrochemistry establishes that the complexes are members of electron transfer series involving a monocation [Re(V)(L(*))(2)(L)](+) (S = 0(?)), a neutral [Re(V)(L(*))(L)(2)](0) (S = 1/2), a monoanion [Re(V)(L)(3)](1-) (S = 0), a dianion [Re(IV)(L)(3)](2-) (S = 1/2), and a trianion [Re(III)(L)(3)](3-) (S = 1(?)). The unique X-band EPR spectrum of the neutral species clearly describes a diamagnetic Re(V) d(2) central ion with the unpaired electron located in a purely ligand-centered molecular orbital, whereas it is metal-centered in the dianionic form: a Re(IV) d(3) ion with three dithiolate(2-) ligands. S K-edge and Re L-edge X-ray absorption spectroscopy confirms these assignments and furthermore shows that the monoanion has a Re(V) central ion with three dianionic ligands. The geometrical and electronic structures of all members of the electron transfer series have been calculated by density functional theoretical methods, and the S K-pre-edge spectra have been simulated and assigned using a time-dependent DFT protocol.

Spectroscopic Studies of the Chan–Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity

We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I) → Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.

One- and Two-Electron Reduced 1,2-Diketone Ligands in [CrIII(L•)3] (S = 0) and Na2(Et2O)2[VIV(LRed)3] (S = 1/2)

The electronic structures of chromium and vanadium centers coordinated by three reduced 1,2-diketones have been elucidated by using density functional theory (DFT) calculations and a host of physical methods: X-ray crystallography; cyclic voltammetry; ultraviolet-visible (UV-vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopy; and magnetic susceptibility measurements. The metal center in octahedral [CrIII(L*)3]0 (1), a CrIII (d3) ion is coupled antiferromagnetically to three monoanionic ligand pi-radicals affording an S ) 0 ground state. In contrast, Na2(Et2O)2[VIV(LRed)3] (2) (S ) 1/2), possesses a central VIV (d1) ion O,OE-coordinated to three closed-shell, doubly reduced ligands which in turn are coordinated by two Na cations enforcing a trigonal prismatic geometry at the vanadium center. 2 can be oxidized electrochemically by one and two electrons generating a monoanion, [V(L)3]1-, and a neutral species, [V(L)3]0, respectively. DFT calculations atthe B3LYP level show that the one-electron oxidized product contains an octahedral VIV ion coupled antiferromagnetically to one monoanionic ligand pi-radical [VIV(L*)(LRed)2]1- (S ) 0). In contrast, the two-electron oxidized product contains a VIII ion coupled antiferromagnetically to three ligand pi-radicals in an octahedral field[VIII(L*)3]0 (S ) 1/2).

Electronic structures of the [V(tbpy)3]z (z = 3+, 2+, 0, 1-) electron transfer series.

The electron transfer series of complexes [V((t)bpy)(3)](z) (z = 3+, 2+, 0, 1-) has been synthesized and spectroscopically characterized with the exception of the monocationic species. Magnetic susceptibility measurements (4-290 K) establish an S = 1 ground state for [V((t)bpy)(3)](3+), S = (3)/(2) for [V((t)bpy)(3)](2+), S = (1)/(2) for [V((t)bpy)(3)], and an S = 0 ground state for [V((t)bpy)(3)](1-). The electrochemistry of this series recorded in tetrahydrofuran solution exhibits four reversible one-electron transfer steps. Electronic absorption, X-band electron paramagnetic resonance (EPR), and V K-edge X-ray absorption (XAS) spectra were recorded. All complexes have been studied computationally with density functional theory (DFT) using the B3LYP functional. It is unequivocally shown that the electronic structure of complexes is best described as [V(III)((t)bpy(0))(3)](3+), [V(II)((t)bpy(0))(3)](2+), [V(II)((t)bpy(•))(2)((t)bpy(0))](0), and [V(II)((t)bpy(•))(3)](1-), where ((t)bpy(0)) represents the neutral form of the ligand and ((t)bpy(•))(1-) is the one-electron reduced mononanionic radical form. In the neutral and monoanionic members, containing two and three ((t)bpy(•))(1-) ligands, respectively, the ligand spins are strongly antiferromagnetically coupled to the spins of the central V(II) ion (d(3); S = (3)/(2)) affording the observed ground states given above.