Styrene Aziridination by Iron(IV) Nitrides.

Thermolysis of the iron(IV) nitride complex [PhB(tBuIm)3Fe≡N] with styrene leads to formation of the high-spin iron(II) aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)]. Similar aziridination occurs with both electron-rich and electron-poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)] acts as a nitride synthon, reacting with electron-poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross-metathesis. Reaction of [PhB(tBuIm)3Fe-N(CH2CHPh)] with Me3SiCl releases the N-functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating [PhB(tBuIm)3FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm)3Fe≡N] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.

Steric and electronic control of the spin state in three-fold symmetric, four-coordinate iron(II) complexes.

The three-fold symmetric, four-coordinate iron(II) phosphoraminimato complexes PhB(MesIm)3Fe-N═PRR'R″ (PRR'R″ = PMePh2, PMe2Ph, PMe3, and P(n)Pr3) undergo a thermally induced S = 0 to S = 2 spin-crossover in fluid solution. Smaller phosphoraminimato ligands stabilize the low-spin state, and an excellent correlation is observed between the characteristic temperature of the spin-crossover (T1/2) and the Tolman cone angle (θ). Complexes with para-substituted triaryl phosphoraminimato ligands (p-XC6H4)3P═N(-) (X = H, Me and OMe) also undergo spin-crossover in solution. These isosteric phosphoraminimato ligands reveal that the low-spin state is stabilized by more strongly donating ligands. This control over the spin state provides important insights for modulating the magnetic properties of four-coordinate iron(II) complexes.

Reaction of an iron(IV) nitrido complex with cyclohexadienes: cycloaddition and hydrogen-atom abstraction.

The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η(5)-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels-Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product.

Cobalt azide complexes with a tris(carbene)borate ligand scaffold.

The four-coordinate Co(II) complex, (azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(II), [Co(C27H38BN6)(N3)], (1), denoted PhB(t-BuIm)3CoN3, was prepared by the reaction of the corresponding chloride complex with NaN3. One-electron oxidation results in the isolation of the five-coordinate Co(III) complex, bis(azido-κN)[1,1,',1''-(phenylboranetriyl)tris(3-tert-butyl-1H-imidazol-2-ylidene)]cobalt(III), [Co(C27H38BN6)(N3)2], (2), denoted PhB(t-BuIm)3Co(N3)2. Attempts to prepare cobalt nitrides by thermolysis or photolysis of these complexes were unsuccessful.

Tuning the reactivity of TEMPO by coordination to a Lewis acid: isolation and reactivity of MCl3(η1-TEMPO) (M = Fe, Al).

Addition of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) to MCl(3) (M = Fe, Al) results in the formation of MCl(3)(η(1)-TEMPO) [M = Fe (1), Al (2)]. Both 1 and 2 oxidize alcohols to generate ketones or aldehydes along with the reduced complexes MCl(3)(η(1)-TEMPOH) [M = Fe (3), Al (4)]. Complexes 1-4 were fully characterized, including analysis by X-ray crystallography. Additionally, control experiments indicated that neither MCl(3) (M = Al, Fe) nor TEMPO are capable of effecting the oxidation of alcohols independently.

Spin crossover in a four-coordinate iron(II) complex.

The four-coordinate iron(II) phosphoraniminato complex PhB(MesIm)(3)Fe-N═PPh(3) undergoes an S = 0 to S = 2 spin transition with T(C) = 81 K, as determined by variable-temperature magnetic measurements and Mössbauer spectroscopy. Variable-temperature single-crystal X-ray diffraction revealed that the S = 0 to S = 2 transition is associated with an increase in the Fe-C and Fe-N bond distances and a decrease in the N-P bond distance. These structural changes have been interpreted in terms of electronic structure theory.

Nitrogen atom transfer from iron(IV) nitrido complexes: a dual-nature transition state for atom transfer.

The mechanism of nitrogen atom transfer from four-coordinate tris(carbene)borate iron(IV) nitrido complexes to phosphines and phosphites has been investigated. In the absence of limiting steric effects, the rate of nitrogen atom transfer to phosphines increases with decreasing phosphine σ-basicity. This trend has been quantified by a Hammett study with para-substituted triarylphosphines, and is contrary to the expectations of an electrophilic nitrido ligand. On the basis of electronic structure calculations, a dual-nature transition state for nitrogen atom transfer is proposed, in which a key interaction involves the transfer of electron density from the nitrido highest occupied molecular orbital (HOMO) to the phosphine lowest unoccupied molecular orbital (LUMO). Compared to analogous atom transfer reactions from a 5d metal, these results show how the electronic plasticity of a 3d metal results in rapid atom transfer from pseudotetrahedral late metal complexes.

Formation of ammonia from an iron nitrido complex.

Radical ideas: Reaction of the iron(IV) nitrido complex [PhB(MesIm)(3)Fe[triple chemical bond]N] (see picture, Mes=2,4,6-Me(3)C(6)H(2)) with TEMPO-H (1-hydroxy-2,2,6,6-tetramethylpiperidine) results in high yields of ammonia and quantitative formation of [PhB(MesIm)(3)Fe(tempo)]. The mechanism likely involves hydrogen-atom transfer from TEMPO-H to the nitrido complex. Similar reaction with the triphenylmethyl radical yields [PhB(MesIm)(3)Fe[triple chemical bond]N--CPh(3)].

Structural and spectroscopic characterization of an electrophilic iron nitrido complex.

We have isolated and structurally characterized a terminal iron nitrido complex supported by a bulky tris(carbene)borate ligand. The electronic structure of this complex reveals that the a1 LUMO (formerly Fe(dz2)) is strongly stabilized by reduced antibonding interactions with the carbene sigma-donor ligands and configurational mixing (hybridization) with higher lying Fe 4s and 4p atomic orbitals. This unusual bonding interaction results in a low-lying Fe nitrido acceptor orbital (LUMO) that possesses electrophilic character. Reaction with PPh3 results in nitrogen atom transfer to the phosphine, supporting a reaction mechanism involving nucleophilic attack of the triphenylphosphine HOMO at the electrophilic LUMO of the iron nitrido complex.

Complexes of Cu(I) supported by a tris(ketimine) tripod.

Arylation of tris(2-benzylnitrile)amine with PhLi, followed by aqueous work-up, results in the formation of a tripodal tris(ketimine) scaffold, N(ArCNHPh)(3). N(ArCNHPh)(3) readily coordinates a number of Cu(I) salts, generating complexes that exhibit trigonal pyramidal geometries in the solid-state.

Synthesis, structure, and reactivity of an iron(V) nitride.

Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. Mößbauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.