Complex PhB Research Articles

A Transient Iron Carbide Generated by Cyaphide Cleavage.

Despite their potential relevance as molecular models for industrial and biological catalysis, well-defined mononuclear iron carbide complexes are unknown, in part due to the limited number of appropriate C1 synthons. Here, we show the ability of the cyaphide anion (C≡P-) to serve as a C1 source. The high spin (S = 2) cyaphide complex PhB(tBuIm)3Fe-C≡P (PhB(tBuIm)3- = phenyl(tris(3-tert-butylimidazol-2-ylidene)borate) is readily accessed using the new cyaphide transfer reagent [Mg(DippNacNac)(CP)]2 (DippNacNac = CH{C(CH3)N(Dipp)}2 and Dipp = 2,6-di(iso-propyl)phenyl). Phosphorus atom abstraction is effected by the three-coordinate Mo(III) complex Mo(NtBuAr)3 (Ar = 3,5-Me2C6H3), which produces the known phosphide (tBuArN)3Mo≡P along with a transient iron carbide complex PhB(tBuIm)3Fe≡C. Electronic structure calculations reveal that PhB(tBuIm)3Fe≡C adopts a doublet ground state with nonzero spin density on the carbide ligand. While isolation of this complex is thwarted by rapid dimerization to afford the corresponding diiron ethynediyl complex, the carbide can be intercepted by styrene to provide an iron alkylidene.

Trimethylsilyldiazomethane Disassembly at a Three-Fold Symmetric Iron Site.

The reaction of equimolar trimethylsilyldiazomethyllithium (LiTMSD) with high spin (S = 2) PhB(AdIm)3FeCl (PhB(AdIm)3- = tris(3-adamantylimidazol-2-ylidene)phenylborate) affords the corresponding N-nitrilimido complex PhB(AdIm)3Fe-N═N═C(SiMe3). This complex can be converted to the thermodynamically more favorable C-isocyanoamido isomer PhB(AdIm)3Fe-C═N═N(SiMe3) by reaction with an additional equivalent of LiTMSD. While the iron(II) complexes are four-coordinate, the diazomethane is bound side-on in the iron(I) congener PhB(AdIm)3Fe(N,N'-κ2-N2C(H)Si(CH3)3). The latter complex adopts high spin (S = 3/2) ground state and features an unusually weak C-H bond. Photolysis of the iron(II) complexes induces N═N bond cleavage, with the iron(II) cyanide PhB(AdIm)3Fe-C≡N and iron(IV) nitride PhB(AdIm)3Fe≡N complexes being the major products of the reaction. The same products are obtained when the iron(I) complex is photolyzed or treated with a fluoride source. The trimethylsilyldiazomethane-derived ligand disassembly reactions are contrasted with those observed for related tris(carbene)amine complexes.

Testing the Limits of Imbalanced CPET Reactivity: Mechanistic Crossover in H-Atom Abstraction by Co(III)-Oxo Complexes.

Transition metal-oxo complexes are key intermediates in a variety of oxidative transformations, notably C-H bond activation. The relative rate of C-H bond activation mediated by transition metal-oxo complexes is typically predicated on substrate bond dissociation free energy in cases with a concerted proton-electron transfer (CPET). However, recent work has demonstrated that alternative stepwise thermodynamic contributions such as acidity/basicity or redox potentials of the substrate/metal-oxo may dominate in some cases. In this context, we have found basicity-governed concerted activation of C-H bonds with the terminal CoIII-oxo complex PhB(tBuIm)3CoIIIO. We have been interested in testing the limits of such basicity-dependent reactivity and have synthesized an analogous, more basic complex, PhB(AdIm)3CoIIIO, and studied its reactivity with H-atom donors. This complex displays a higher degree of imbalanced CPET reactivity than PhB(tBuIm)3CoIIIO with C-H substrates, and O-H activation of phenol substrates displays mechanistic crossover to stepwise proton transfer-electron transfer (PTET) reactivity. Analysis of the thermodynamics of proton transfer (PT) and electron transfer (ET) reveals a distinct thermodynamic crossing point between concerted and stepwise reactivity. Furthermore, the relative rates of stepwise and concerted reactivity suggest that maximally imbalanced systems provide the fastest CPET rates up to the point of mechanistic crossover, which results in slower product formation.

Facile Addition of B-H and B-B Bonds to an Iron(IV) Nitride Complex.

The nitride ligand in the iron(IV) complex PhB(iPr2Im)3Fe≡N reacts with boron hydrides to afford PhB(iPr2Im)3FeN(B)H (B = 9-BBN (1), Bpin (2)) and with (Bpin)2 to afford PhB(iPr2Im)3FeN(Bpin)2 (3). The iron(II) borylamido products have all been structurally and spectroscopically characterized, demonstrating facile insertion into B-H and B-B bonds by PhB(iPr2Im)3Fe≡N. Density functional theory (DFT) calculations reveal that the quintet state (S = 2) is significantly lower in energy than the singlet (S = 0) and triplet (S = 1) states for all products. Stoichiometric reaction with (Bpin)2 does not produce the mono-borylated iron imido species PhB(iPr2Im)3FeN(Bpin). DFT calculations suggest that this is because PhB(iPr2Im)3FeN(Bpin) is unstable toward disproportionation to the starting iron(IV) nitride and PhB(iPr2Im)3FeN(Bpin)2. Attempts at B-C bond insertion using phenyl- and benzyl-pinacol borane were unsuccessful, which we attribute to unfavorable kinetics.

Synthesis and reactivity of a tris(carbene) zinc chloride complex.

The [PhB(tBuIm)3]1- ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The PhB(tBuIm)3ZnCl (1) complex can be formed via deprotonation of [PhB(tBuIm)3][OTf]2 followed by the addition of ZnCl2. Salt metathesis reaction with nucleophilic n-BuLi yields the highly carbon-rich zinc coordination complex PhB(tBuIm)3ZnBu (2) with three carbene atom donors and one carbanion donor. In contrast, reaction of complex 1 with a less nucleophilic polysulfide reagent, [K.18-C-6]2[S4], leads to the formation of a tetrahedral zinc tetrasulfido complex via protonation of one carbene donor to form PhB(tBuIm)2(tBuImH)Zn(κ2-S4) (3).

Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex.

The iron oxo unit, [Fe=O]n+ is a critical intermediate in biological oxidation reactions. While its higher oxidation states are well studied, relatively little is known about the least-oxidized form [FeIII=O]+. Here, the thermally stable complex PhB(AdIm)3Fe=O has been structurally, spectroscopically, and computationally characterized as a bona fide iron(III) oxo. An unusually short Fe–O bond length is consistent with iron–oxygen multiple bond character and is supported by electronic structure calculations. The complex is thermally stable yet is able to perform hydrocarbon oxidations, facilitating both C–O bond formation and dehydrogenation reactions.

Hydrosilylation of an Iron(IV) Nitride Complex.

The nitride ligand in iron(IV) complex PhB(MesIm)3Fe≡N reacts with excess H3SiPh to afford PhB(MesIm)3Fe(μ-H)3(SiHPh) as the major product, which has been structurally and spectroscopically characterized. Bulkier silane HaSiPh2 provides iron(II) amido complex PhB(MesIm)3FeN(H)(SiHPh2) as the initial product of the reaction, with excess H2SiPh2 affording diamagnetic PhB(MesIm)3Fe(μ-H)3(SiPh2) as the major product. Unobserved iron(II) hydride PhB(MesIm)3Fe-H is implicated as an intermediate in this reaction, as suggested by the results of the reaction between iron(II) amido PhB(MesIm)3FeN(H)tBu and H3SiPh, which provides PhB(MesIm)3Fe(H)(μ-H)2(Si(NHtBu)Ph) as the sole product.

Strong π-Backbonding Enables Record Magnetic Exchange Coupling Through Cyanide.

The paramagnetic cyano-bridged complex PhB(tBuIm)3Fe-NC-Mo(NtBuAr)3 (Ar = 3,5-Me2C6H3) is readily assembled from a new four-coordinate, high-spin (S = 2) iron(II) monocyanide complex and the three-coordinate molybdenum(III) complex Mo(NtBuAr)3. X-ray diffraction and IR spectroscopy reveal that delocalization of unpaired electron density into the cyanide π* orbitals leads to a reduction of the C-N bond order. Direct current (dc) magnetic susceptibility measurements, supported by electronic structure calculations, demonstrate the presence of strong antiferromagnetic exchange between spin centers, with a coupling constant of J = -122(2) cm-1. To our knowledge, this value represents the strongest magnetic exchange coupling ever to be observed through cyanide. These results demonstrate the ability of low-coordinate metal fragments to engender extremely strong magnetic exchange coupling through cyanide by virtue of significant π-backbonding into the cyanide ligand.

Experimental Evidence for p Ka-Driven Asynchronicity in C-H Activation by a Terminal Co(III)-Oxo Complex.

C-H activation by transition metal oxo complexes is a fundamental reaction in oxidative chemistry carried out by both biological and synthetic systems. This centrality has motivated efforts to understand the patterns and mechanisms of such reactivity. We have therefore thoroughly examined the C-H activation reactivity of the recently synthesized and characterized late transition metal oxo complex PhB ( tBuIm)3CoIIIO. Precise values for the p Ka and BDFEO-H of the conjugates of this complex have been experimentally determined and provide insight into the observed reactivity. The activation parameters for the reaction between this complex and 9,10-dihydroanthracene have also been measured and compared to previous literature examples. Evaluation of the rates of reaction of PhB( tBuIm)3CoIIIO with a variety of hydrogen atom donors demonstrates that the reactivity of this complex is dependent on the p Ka of the substrate of interest rather than the BDEC-H. This observation runs counter to the commonly cited reactivity paradigm for many other transition metal oxo complexes. Experimental and computational analysis of C-H activation reactions by PhB( tBuIm)3CoIIIO reveals that the transition state for these processes contains significant proton transfer character. Nevertheless, additional experiments strongly suggest that the reaction does not occur via a stepwise process, leading to the conclusion that C-H activation by this CoIII-oxo complex proceeds by a p Ka-driven "asynchronous" concerted mechanism. This result supports a new pattern of reactivity that may be applicable to other systems and could result in alternative selectivity for C-H activation reactions mediated by transition metal oxo complexes.

Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride.

The new iron(IV) nitride complex PhB(iPr2Im)3Fe≡N reacts with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB(iPr2Im)3Fe(CN)(N2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr2N-C≡C-NiPr2. The iron complex is in equilibrium with an N2-free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C6F5)3 provides the cyanoborane derivative.

Arrested α-hydride migration activates a phosphido ligand for C-H insertion.

Bulky tris(carbene)borate ligands provide access to high spin iron(ii) phosphido complexes. The complex PhB(MesIm)3FeP(H)Ph is thermally unstable, and [PPh] group insertion into a C-H bond of the supporting ligand is observed. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

Low-Valent Iron Carbonyl Complexes with a Tripodal Carbene Ligand

A bulky tris(carbene)borate ligand allows several low-valent iron carbonyl complexes to be isolated. One-electron reduction of the cationic iron(II) complex [PhB(MesIm)3Fe(CO)3][B(C6F5)4] (1) ([PhB(MesIm3)]− = phenyltris(1-mesitylimidazol-2-ylidene)borate) yields the low-spin (S = 1/2) iron(I) complex PhB(MesIm)3Fe(CO)2 (2), as determined by structural and spectroscopic methods. This complex can in turn be reduced to provide the anionic dicarbonyl complex [K][PhB(MesIm)3Fe(CO)2] (3), which crystallizes as a dimer in which the potassium cation coordinates in a side-on fashion to one CO ligand. Protonation of 3 yields the weakly acidic iron hydride PhB(MesIm)3Fe(CO)2H (4), which can also be isolated by treating the κ3-coordinated alkylborohydrido complex PhB(MesIm)3Fe(κ3-BH(CH2CH3)3) (5) with CO. The strong donor ability of the tris(carbene)borate ligand results in significant reduction of the CO bonds, as measured by IR spectroscopy.

Partial Nitrogen Atom Transfer: A New Synthetic Tool to Design Single-Molecule Magnets

Incomplete nitrogen atom transfer from the iron(IV) nitride complex PhB(MesIm)3Fe≡N to the vanadium(III) complex V(Mes)3(THF) quantitatively provides the bimetallic complex PhB(MesIm)3Fe-N═V(Mes)3. Structural and spectroscopic characterizations reveal that the nitride ligand forms a linear bridge between V(V) and high-spin Fe(II) metal ions, confirming that atom transfer is accompanied by electron transfer. In the presence of an applied dc field, the complex displays slow relaxation of the magnetization, revealing its single-molecule magnet properties with an estimation of the energy barrier at about 10 K. This complex establishes a synthetic principle for the assembly of paramagnetic complexes bridged by nitride ligands.

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(η5-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.

N–O Bond Homolysis of an Iron(II) TEMPO Complex Yields an Iron(III) Oxo Intermediate

The reaction of TEMPO with the iron(I) synthon PhB(MesIm)(3)Fe(COE) leads to formation of the κ(1)-TEMPO complex PhB(MesIm)(3)Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis of the complex results in N-O bond homolysis, leading to the formation of an iron(III) oxo intermediate. The oxo intermediate is active in oxygen atom transfer reactions and can be trapped by the triphenylmethyl radical to give the iron(II) alkoxo complex PhB(MesIm)(3)Fe(OCPh(3)).

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.

Oxidation of the Tris(carbene)borate Complex PhB(MeIm)3MnI(CO)3 to MnIV[PhB(MeIm)3]2(OTf)2

Reaction of the tris(carbene)borate ligand PhB(MeIm)3- with [Mn(CO)3(tBuCN)Br]2 leads to the manganese(I) tricarbonyl complex PhB(MeIm)3Mn(CO)3. In contrast to related complexes that are air-stable, PhB(MeIm)3Mn(CO)3 is O2-sensitive and is converted to a homoleptic MnIV complex. IR and cyclic voltammetry measurements of these complexes establish the exceptionally strong donating nature of the tris(carbene)borate ligand.

New Examples of Half-Sandwich (Borylcyclopentadienyl)titanium Trichloride Complexes and an X-ray Structural Characterization of the Homobimetallic Complex [TiCl3{η5-C5H4}]2BPh

A new series of half-sandwich (borylcyclopentadienyl)titanium trichloride complexes have been prepared which include the boryl substituents [1,2-(C6H4O2)]B−, Ph(Cl)B−, Ph2B− and a (PhB<)-bridged bimetallic complex. No correlation was found between the 1H and 13C NMR chemical shifts of the cyclopentadienyl ring in these complexes and the Lewis acidity of the attached boryl group. The crystal structure of the phenylboron-bridged bimetallic complex PhB{(η5-C5H4)TiCl3}2 was determined. The cyclopentadienyltitanium units of the molecule are twisted away from each other, forming an angle of 41° between the cyclopentadienyl ring planes. Each cyclopentadienyl ring is twisted out of the trigonal plane of the boron by 24°. Preliminary results concerning the Ti-alkylation of some of these complexes are described.