Molybdenum chalcogenobenzimidato complexes: radical synthesis and nitrile extrusion via beta-EPh (E = S, Se, and Te) elimination

Molybdenum chalcogenobenzimidates of formula (Ph[PhE]C=N)Mo(N[t-Bu]Ar)(3) (Ar = 3,5-C(6)H(3)Me(2)) have been obtained by treatment of Mo(N[t-Bu]Ar)(3) sequentially with benzonitrile and 0.5 equiv of PhEEPh (E = S, Se, and Te). Molecular structure determinations have been carried out for the S and Se variants. The Te variant extrudes PhCN forming structurally characterized (PhTe)Mo(N[t-Bu]Ar)(3) with facility assessed via stopped-flow kinetic measurements, while the Se and S analogues exhibit increasing stability. Quantum chemical calculations and solution calorimetry have been employed as an aid to interpretation of the PhCN extrusion reaction.     

A cycle for organic nitrile synthesis via dinitrogen cleavage

In the presence of NaH, the reaction between N2 and Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) proceeds at room temperature to afford NMo(N[t-Bu]Ar)3 (95%). Lewis acidic silyl triflates (Me3SiOTf + pyridine or (i-Pr)3SiOTf) mediate a reaction between acid chlorides and NMo(N[t-Bu]Ar)3 to yield acyl imidos [RC(O)NMo(N[t-Bu]Ar)3][OTf] (R = Me, 92%; Ph, 75%; t-Bu, 64%). The reduction of [RC(O)NMo(N[t-Bu]Ar)3][OTf] by magnesium anthracene followed by treatment with Me3SiOTf affords molybdenum ketimides, R(Me3SiO)CNMo(N[t-Bu]Ar)3 (R = Me, 82%; Ph, 77%; t-Bu, 46%). Exposing R(Me3SiO)CNMo(N[t-Bu]Ar)3 to SnCl2 or ZnCl2 produces ClMo(N[t-Bu]Ar)3 (71-93% for SnCl2) and RCN (97-99%). Magnesium metal reduces ClMo(N[t-Bu]Ar)3 to Mo(N[t-Bu]Ar)3 (74%), completing a synthetic cycle. New strategies for the functionalization of sterically hindered nitrides and nitrile extrusion from d2 ketimides are presented in the context of a new route for derivatizing N2.     

A nitridoniobium(V) reagent that effects acid chloride to organic nitrile conversion: synthesis via heterodinuclear (Nb/Mo) dinitrogen cleavage, mechanistic insights, and recycling

The transformation of acid chlorides (RC(O)Cl) to organic nitriles (RC[triple bond]N) by the terminal niobium nitride anion [N[triple bond]Nb(N[Np]Ar)3]- ([1a-N]-, where Np = neopentyl and Ar = 3,5-Me2C6H3) via isovalent N for O(Cl) metathetical exchange is presented. Nitrido anion [1a-N]- is obtained in a heterodinuclear N2 scission reaction employing the molybdenum trisamide system, Mo(N[R]Ar)3 (R = t-Bu, 2a; R = Np, 2b), as a reaction partner. Reductive scission of the heterodinuclear bridging N2 complexes, (Ar[R]N)3Mo-(mu-N2)Nb(N[Np]Ar)3 (R = t-Bu, 3b; R = Np, 3c) with sodium amalgam provides 1 equiv each of the salt Na[1a-N] and neutral N[triple bond]Mo(N[R]Ar)3 (R = t-Bu, 2a-N; R = Np, 2b-N). Separation of 2-N from Na[1a-N] is readily achieved. Treatment of salt Na[1a-N] with acid chloride substrates in tetrahydrofuran (THF) furnishes the corresponding organic nitriles concomitant with the formation of NaCl and the oxo niobium complex O[triple bond]Nb(N[Np]Ar)3 (1a-O). Utilization of 15N-labeled 15N2 gas in this chemistry affords a series of 15N-labeled organic nitriles establishing the utility of anion [1a-N]- as a reagent for the 15N-labeling of organic molecules. Synthetic and computational studies on model niobium systems provide evidence for the intermediacy of both a linear acylimido and niobacyclobutene species along the pathway to organic nitrile formation. High-yield recycling of oxo 1a-O to a niobium triflate complex appropriate for heterodinuclear N2 scission has been developed. Specifically, addition of triflic anhydride (Tf2O, where Tf = SO2CF3) to an Et2O solution of 1a-O provides the bistriflate complex, Nb(OTf)2(N[Np]Ar)3 (1a-(OTf)2), in near quantitative yield. One-electron reduction of 1a-(OTf)2 with either cobaltocene (Cp2Co) or Mg(THF)3(anthracene) provided the monotriflato complex, Nb(OTf)(N[Np]Ar)3 (1a-(OTf)), which efficiently regenerates complexes 3b and 3c when treated with the molybdenum dinitrogen anions [N2Mo(N[t-Bu]Ar)3]- ([2a-N2]-) or [N2Mo(N[Np]Ar)3]- ([2b-N2]-), respectively.     

Heterobimetallic reductive cross-coupling of benzonitrile with carbon dioxide, pyridine, and benzophenone

Described herein are heterobimetallic radical cross-coupling reactions between the benzonitrile adduct of the molybdenum(III) complex Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) and titanium(III) complexes with carbon dioxide, pyridine, and benzophenone. The titanium(III) system employed was either Ti(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) or Ti(N[t-Bu]Ph)3. Crystal structure studies are described for the Mo/PhCN/CO2/Ti coupled system and for an analogue of the Mo/PhCN/Ph2CO/Ti coupled system in which PhCN is replaced with 2,6-Me2C6H3CN. In the case of the couplings involving pyridine and benzophenone, C-C bond formation takes place with dearomatization, with the new C-C bond being formed between the nitrile carbon of PhCN and the para carbon of pyridine or one of the benzophenone phenyl groups. Of the radical metal complex/substrate adducts invoked in this work, that between titanium(III) and CO2 is the only one not directly observable. In all cases, the selective cross-coupling reactions are interpreted as arising by heterodimerization of titanium(III) substrate complexes (substrate = CO2, py, or Ph2CO) with the persistent molybdenum-PhCN radical adduct. All of the heterobimetallic coupling products are diamagnetic, and the metal ions Ti and Mo in them both are assigned to the formal 4+ oxidation state.     

In pursuit of the molybdenum(III) tris(thiolate) fragment: unusual structure of a dimolybdenum mu-nitrido complex

The new molybdenum nitrido-thiolate complex N triple bond Mo(SAd)3 (Ad = 1-adamantyl) was prepared by a ligand exchange route involving reaction of Ti(SAd)(OiPr)3 with Chisholm's nitrido-butoxide complex N triple bond Mo(OtBu)3. In an effort to abstract the nitrido nitrogen from N triple bond Mo(SAd)3, the compound was treated with Mo(N[tBu]Ph)3, a three-coordinate molybdenum(III) complex. This resulted in formation of the unusual and thermally unstable (mu-nitrido)dimolybdenum complex (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3, which was isolated and characterized. An X-ray study revealed (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3 to possess an unsymmetrical Mo-(mu-N)-Mo linkage, the Mo-thiolate fragment exhibiting a substantially longer bond to the bridging nitrogen atom. The structure of (AdS)3Mo-(mu-N)Mo(N[tBu]Ph)3 is noteworthy, displaying trigonal monopyramidal coordination at the (mu-N)-Mo-thiolate Mo center. Since N triple bond Mo(N[tBu]Ph)3 is a good leaving group, (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3 should be a source of the reactive Mo(SAd)3 fragment. In all the studied reactions of the (mu-nitrido)dimolybdenum complex one of the observed products was N triple bond Mo(N[tBu]Ph)3. Two products containing the Mo(SAd)3 fragment were observed: (AdS)3Mo triple bond Mo(SAd)3 and [(ON)Mo(mu-SAd)(SAd)2]2. Upon treatment with pyridine, the tris(thio-1-adamantyl)-(nitrosyl)molybdenum dimer forms the pyridine adduct (AdS)3Mo(NO)(py), which is a monomer.     

Thermodynamic and kinetic studies of H atom transfer from HMo(CO)3(eta(5)-C5H5) to Mo(N[t-Bu]Ar)3 and (PhCN)Mo(N[t-Bu]Ar)3: direct insertion of benzonitrile into the Mo-H bond of HMo(N[t-Bu]Ar)3 forming (Ph(H)C=N)Mo(N[t-Bu]Ar)3

Synthetic studies are reported that show that the reaction of either H2SnR2 (R = Ph, n-Bu) or HMo(CO)3(Cp) (1-H, Cp = eta(5)-C5H5) with Mo(N[t-Bu]Ar)3 (2, Ar = 3,5-C6H3Me2) produce HMo(N[t-Bu]Ar)3 (2-H). The benzonitrile adduct (PhCN)Mo(N[t-Bu]Ar)3 (2-NCPh) reacts rapidly with H2SnR2 or 1-H to produce the ketimide complex (Ph(H)C=N)Mo(N[t-Bu]Ar)3 (2-NC(H)Ph). The X-ray crystal structures of both 2-H and 2-NC(H)Ph are reported. The enthalpy of reaction of 1-H and 2 in toluene solution has been measured by solution calorimetry (DeltaH = -13.1 +/- 0.7 kcal mol(-1)) and used to estimate the Mo-H bond dissociation enthalpy (BDE) in 2-H as 62 kcal mol(-1). The enthalpy of reaction of 1-H and 2-NCPh in toluene solution was determined calorimetrically as DeltaH = -35.1 +/- 2.1 kcal mol(-1). This value combined with the enthalpy of hydrogenation of [Mo(CO)3(Cp)]2 (1(2)) gives an estimated value of 90 kcal mol(-1) for the BDE of the ketimide C-H of 2-NC(H)Ph. These data led to the prediction that formation of 2-NC(H)Ph via nitrile insertion into 2-H would be exothermic by approximately 36 kcal mol(-1), and this reaction was observed experimentally. Stopped flow kinetic studies of the rapid reaction of 1-H with 2-NCPh yielded DeltaH(double dagger) = 11.9 +/- 0.4 kcal mol(-1), DeltaS(double dagger) = -2.7 +/- 1.2 cal K(-1) mol(-1). Corresponding studies with DMo(CO)3(Cp) (1-D) showed a normal kinetic isotope effect with kH/kD approximately 1.6, DeltaH(double dagger) = 13.1 +/- 0.4 kcal mol(-1) and DeltaS(double dagger) = 1.1 +/- 1.6 cal K(-1) mol(-1). Spectroscopic studies of the much slower reaction of 1-H and 2 yielding 2-H and 1/2 1(2) showed generation of variable amounts of a complex proposed to be (Ar[t-Bu]N)3Mo-Mo(CO)3(Cp) (1-2). Complex 1-2 can also be formed in small equilibrium amounts by direct reaction of excess 2 and 1(2). The presence of 1-2 complicates the kinetic picture; however, in the presence of excess 2, the second-order rate constant for H atom transfer from 1-H has been measured: 0.09 +/- 0.01 M(-1) s(-1) at 1.3 degrees C and 0.26 +/- 0.04 M(-1) s(-1) at 17 degrees C. Study of the rate of reaction of 1-D yielded kH/kD = 1.00 +/- 0.05 consistent with an early transition state in which formation of the adduct (Ar[t-Bu]N)3Mo...HMo(CO)3(Cp) is rate limiting.     

Thermodynamic, kinetic, and computational study of heavier chalcogen (S, Se, and Te) terminal multiple bonds to molybdenum, carbon, and phosphorus

Enthalpies of chalcogen atom transfer to Mo(N[t-Bu]Ar)3, where Ar = 3,5-C6H3Me2, and to IPr (defined as bis-(2,6-isopropylphenyl)imidazol-2-ylidene) have been measured by solution calorimetry leading to bond energy estimates (kcal/mol) for EMo(N[t-Bu]Ar)3 (E = S, 115; Se, 87; Te, 64) and EIPr (E = S, 102; Se, 77; Te, 53). The enthalpy of S-atom transfer to PMo(N[ t-Bu]Ar) 3 generating SPMo(N[t-Bu]Ar)3 has been measured, yielding a value of only 78 kcal/mol. The kinetics of combination of Mo(N[t-Bu]Ar)3 with SMo(N[t-Bu]Ar)3 yielding (mu-S)[Mo(N[t-Bu]Ar)3]2 have been studied, and yield activation parameters Delta H (double dagger) = 4.7 +/- 1 kcal/mol and Delta S (double dagger) = -33 +/- 5 eu. Equilibrium studies for the same reaction yielded thermochemical parameters Delta H degrees = -18.6 +/- 3.2 kcal/mol and Delta S degrees = -56.2 +/- 10.5 eu. The large negative entropy of formation of (mu-S)[Mo(N[t-Bu]Ar)3]2 is interpreted in terms of the crowded molecular structure of this complex as revealed by X-ray crystallography. The crystal structure of Te-atom transfer agent TePCy3 is also reported. Quantum chemical calculations were used to make bond energy predictions as well as to probe terminal chalcogen bonding in terms of an energy partitioning analysis.     

Imidomolybdenum(IV) porphyrin complexes: synthesis, characterization, and intermetal imido transfer reactivity

The imido(meso-tetra-p-tolylporphyrinato)molybdenum(IV) complexes, (TTP)Mo=NR, where R = C6H5 (1a), p-CH3C6H4 (1b), 2,4,6-(CH3)3C6H2 (1c), and 2,6-(i-Pr)2C6H4 (1d), can be prepared by the reaction of (TTP)MoCl2 with 2 equiv of LiNHR in toluene. Upon treatment of the imido complexes with pyridine derivatives, NC5H4-p-X (X = CH3, CH(CH3)2, C[triple bond]N), new six-coordinate complexes, (TTP)Mo=NR.NC5H4-p-X, were observed. The reaction between the molybdenum imido complexes, (TTP)Mo=NC6H5 or (TTP)Mo=NC6H4CH3, and (TTP)Ti(eta2-PhC[triple bond]CPh) resulted in complete imido group transfer and two-electron redox of the metal centers to give (TTP)Mo(eta2-PhC[triple bond]CPh) and (TTP)Ti=NC6H5 or (TTP)Ti=NC6H4CH3.     

Shining light on dinitrogen cleavage: structural features, redox chemistry, and photochemistry of the key intermediate bridging dinitrogen complex

The key intermediate in dinitrogen cleavage by Mo(N[t-Bu]Ar)3, 1 (Ar = 3,5-C6H3Me2), has been characterized by a pair of single crystal X-ray structures. For the first time, the X-ray crystal structure of (mu-N2)[Mo(N[t-Bu]Ar)3]2, 2, and the product of homolytic fragmentation of the NN bond, NMo(N[t-Bu]Ar)3, are reported. The structural features of 2 are compared with previously reported EXAFS data. Moreover, contrasts are drawn between theoretical predictions concerning the structural and magnetic properties of 2 and those reported herein. In particular, it is shown that 2 exists as a triplet (S = 1) at 20 degrees C. Further insight into the bonding across the MoNNMo core of the molecule is obtained by the synthesis and structural characterization of the one- and two-electron oxidized congeners, (mu-N2)[Mo(N[t-Bu]Ar)3]2[B(Ar(F))4], 2[B(Ar(F))4] (Ar(F) = 3,5-C6H3(CF3)2) and (mu-N2)[Mo(N[t-Bu]Ar)3]2[B(Ar(F))4]2, 2[B(Ar(F))4]2, respectively. Bonding in these three molecules is discussed in view of X-ray crystallography, Raman spectroscopy, electronic absorption spectroscopy, and density functional theory. Combining X-ray crystallography data with Raman spectroscopy studies allows the NN bond polarization energy and NN internuclear distance to be correlated in three states of charge across the MoNNMo core. For 2[B(Ar(F))4], bonding is symmetric about the mu-N2 ligand and the NN polarization is Raman active; therefore, 2[B(Ar(F))4] meets the criteria of a Robin-Day class III mixed-valent compound. The redox couples that interrelate 2, 2(+), and 2(2+) are studied by cyclic voltammetry and spectroelectrochemistry. Insights into the electronic structure of 2 led to the discovery of a photochemical reaction that forms NMo(N[t-Bu]Ar)3 and Mo(N[t-Bu]Ar)3 through competing NN bond cleavage and N2 extrusion reaction pathways. The primary quantum yield was determined to be Phi(p) = 0.05, and transient absorption experiments show that the photochemical reaction is complete in less than 10 ns.     

beta-Diiminato ligand (L) transformations in reactions of KL with PI3 and I2 [L = {N(C6H3Pr(i)2-2,6)C(H)}2CPh

The reaction of the potassium beta-diiminate KL (L = [{N(Ar)C(H)}(2)CPh](-); Ar = C(6)H(3)Pr(i)(2)-2,6) with PI(3) unexpectedly produced a phosphenium salt of the intermolecularly C,C-coupled ligand [P(I){N(Ar)CH}(2)C(C(6)H(4)-4)C(Ph)(CH[double bond, length as m-dash]NAr)(2)](+)[I(3)](-), while an intramolecularly N,N-coupled salt [N[upper bond 1 start](Ar)C(H)C(Ph)C(H)N[upper bond 1 end](Ar)](+)[I(5)](-) was isolated from KL + I(2).     

Competitive ArC-H and ArC-X (X = Cl, Br) activation in halobenzenes at cationic titanium centers

The titanium methyl cation [Cp*((tBu3P=N)TiCH3]+ [B(C6F5)4]- reacts rapidly with H2 to give the analogous cationic hydride [Cp*((tBu3P=N)TiH(THF)n]+ [B(C6F5)4]- (n = 0, 1), which can be trapped and isolated as its THF adduct 1 x THF (n = 1). When generated in the presence of chloro or bromobenzene, 1 undergoes C-X activation or ortho-C-H activation, depending on the amount of dihydrogen present in the reaction medium. At approximately 4 atm of H2, C-X activation is preferred, giving the halocations [Cp*((tBu3P= N)TiX]+ [B(C6F5)4]- (2X) and C6H6/biphenyl mixtures. At lower pressures of H2 (>1 atm), the beta-halophenyl cations [Cp*((tBu3P=N)Ti(2-X-C6H4)]+ [B(C6F5)4]- (3X) are the products isolated. In the absence of H2, these compounds are quite thermally stable, but undergo beta-halogen elimination upon moderate heating, to give 2X (approximately 20%) and compounds 4X which are the result of reaction between 2X and benzyne via addition of the benzyne C-C triple bond across the Ti-N bond of the phosphinimide ligand. Thus, three separate bond activation processes are operative in this system: direct C-X activation, ortho-C-H activation, and indirect C-X activation via beta-halogen elimination. Mechanistic studies on all three processes have been done and support a radical pathway for direct C-X cleavage, sigma-bond metathesis of the ortho-C-H bond of eta(1)-coordinated C6H5X, and beta-halogen elimination from base-free compound 3X.     

On the origin of selective nitrous oxide N-N bond cleavage by three-coordinate molybdenum(III) complexes

Reaction of Mo(N[R]Ar)(3) (R = (t)Bu or C(CD(3))(2)CH(3)) with N(2)O gives rise exclusively to a 1:1 mixture of nitride NMo(N[R]Ar)(3) and nitrosyl ONMo(N[R]Ar)(3), rather than the known oxo complex OMo(N[R]Ar)(3) and dinitrogen. Solution calorimetry measurements were used to determine the heat of reaction of Mo(N[R]Ar)(3) with N(2)O and, independently, the heat of reaction of Mo(N[R]Ar)(3) with NO. Derived from the latter measurements is an estimate (155.3 +/- 3.3 kcal.mol(-1)) of the molybdenum-nitrogen bond dissociation enthalpy for the terminal nitrido complex, NMo(N[R]Ar)(3). Comparison of the new calorimetry data with those obtained previously for oxo transfer to Mo(N[R]Ar)(3) shows that the nitrous oxide N-N bond cleavage reaction is under kinetic control. Stopped-flow kinetic measurements revealed the reaction to be first order in both Mo(N[R]Ar)(3) and N(2)O, consistent with a mechanism featuring post-rate-determining dinuclear N-N bond scission, but also consistent with cleavage of the N-N bond at a single metal center in a mechanism requiring the intermediacy of nitric oxide. The new 2-adamantyl-substituted molybdenum complex Mo(N[2-Ad]Ar)(3) was synthesized and found also to split N(2)O, resulting in a 1:1 mixture of nitrosyl and nitride products; the reaction exhibited first-order kinetics and was found to be ca. 6 times slower than that for the tert-butyl-substituted derivative. Discussed in conjunction with studies of the 2-adamantyl derivative Mo(N[2-Ad]Ar)(3) is the role of ligand-imposed steric constraints on small-molecule, e.g. N(2) and N(2)O, activation reactivity. Bradley's chromium complex Cr(N(i)Pr(2))(3) was found to be competitive with Mo(N[R]Ar)(3) for NO binding, while on its own exhibiting no reaction with N(2)O. Competition experiments permitted determination of ratios of second-order rate constants for NO binding by the two molybdenum complexes and the chromium complex. Analysis of the product mixtures resulting from carrying out the N(2)O cleavage reactions with Cr(N(i)Pr(2))(3) present as an in situ NO scavenger rules out as dominant any mechanism involving the intermediacy of NO. Simplest and consistent with all the available data is a post-rate-determining bimetallic N-N scission process. Kinetic funneling of the reaction as indicated is taken to be governed by the properties of nitrous oxide as a ligand, coupled with the azophilic nature of three-coordinate molybdenum(III) complexes.     

The (Calix[4]arene)chloromolybdate(IV) anion [MoCl(Calix)](-): a convenient entry into molybdenum Calix[4]arene chemistry

The complex (HNEt(3))[MoCl(NCMe)(Calix)] (1), prepared from the reaction of [MoCl(4)(NCMe)(2)] with p-tert-butylcalix[4]arene, H(4)Calix, in the presence of triethylamine, has been used as a source of the d(2)-[Mo(NCMe)(Calix)] fragment. Complex 1 is readily oxidized with PhICl(2) to afford the molybdenum(VI) dichloro complex [MoCl(2)(Calix)] (2). Both complexes are a convenient entry point into molybdenum(VI) and molybdenum(IV) calixarene chemistry. The reaction of 1 with trimethylphosphine and pyridine in the presence of catalytic amounts [Ag(OTf)] led to the formation of neutral d(2) complexes [Mo(PMe(3))(NCMe)(Calix)] (3) and [Mo(NC(5)H(5))(NCMe)(Calix)] (4). The role of the silver salt in the reaction mixture is presumably the oxidation of the chloromolybdate anion of 1 to give a reactive molybdenum(V) species. The same reactions can also be initiated with ferrocenium cations such as [Cp(2)Fe](BF(4)). Without the presence of coordinating ligands, the dimeric complex [[Mo(NCMe)(Calix)](2)] (5) was isolated. The reaction of 1 with Ph(2)CN(2) led to the formation of a metallahydrazone complex [Mo(N(2)CPh(2))(NCMe)(Calix)] (6), in which the diphenyldiazomethane has been formally reduced by two electrons. Molybdenum(VI) complexes were also obtained from reaction of 1 with azobenzene and sodium azide in the presence of catalytic amounts of silver salt. The reaction with azobenzene led under cleavage of the nitrogen nitrogen bond to an imido complex [Mo(NPh)(NCMe)(Calix)] (7), whereas the reaction with sodium azide afforded the mononuclear molybdenum(VI) nitrido complex (HNEt(3))[MoN(Calix)] (8).     

Transformation of organic molecules on the low-valent [M(Ph(2)PCH(2)CH(2)PPh(2))(2)] moiety derived from trans-[M(N(2))(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] or related complexes (M = Mo, W)

A zero-valent [M(Ph(2)PCH(2)CH(2)PPh(2))(2)] moiety (M = Mo, W) generated in situ by dissociation of the N(2) ligands in trans-[M(N(2))(2)(Ph(2)PCH(2)CH(2)PPh(2))(2)] can activate pi-accepting organic molecules including isocyanides and nitriles, which undergo the electrophilic attack caused by a strong pi-donation from a zero-valent metal center. Cleavage of a variety of C-X bonds (X = H, C, N, O, P, halogen) also occurs at their electron-rich sites through oxidative addition to form reactive intermediates, which subsequently degradate to yield smaller molecules either bound to or dissociated from the metal center. The mechanism is substantiated unambiguously by isolation of numerous intermediate stages.     

Structural consequences of the one-electron reduction of d4 [Mo(CO)2(eta-PhC[triple bond]CPh)Tp']+ and the electronic structure of the d5 radicals [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {L = CO and P(OCH2)3CEt}

Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis.     

Cyanide-bridged linkage isomers with catecholateruthenium(II) centres bound to Mn(I) or M(alkyne) units

Two series of stable cyanide-bridged linkage isomers, namely [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] (XY = CN or NC, L = CNBu(t) or CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC-CPh)Tp'] {M = Mo or W, L = PPh3 or P(OPh)3, Tp' = hydrotris(3,5-dimethylpyrazolyl)borate} have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry. The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-NC)Mo(CO)(PhC-CPh)Tp'] has the catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhC[triple band]CPh)Tp' unit in which the alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo-CO vector suggests the fragment (CN)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a pi-acceptor ligand. The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)Mn(NO)L(eta-C5Me5)] undergo three sequential one-electron oxidation processes with the first and third assigned to oxidation of the ruthenium-bound o-O2C6Cl4 ligand; the second corresponds to oxidation of Mn(I) to Mn(n). The complexes [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron reduction, are based on the M(CO)(PhC[triple band]CPh)Tp' fragment. Chemical oxidation of [(o-O,C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] with [Fe(eta-C5H4COMe)(eta-C5H5)][BF4], or of [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] with AgBF4, gave the paramagnetic monocations [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)]+ and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp']+, the ESR spectra of which are consistent with ruthenium-bound semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the 31P hyperfine coupling constant; complexes with N-bound Ru(o-O2C6Cl4) units also show small hyperfine coupling to the nitrogen atom of the cyanide bridge.     

Electronic structure, spectroscopic properties, and reactivity of molybdenum and tungsten nitrido and imido complexes with diphosphine coligands: influence of the trans ligand

A series of molybdenum and tungsten nitrido, [M(N)(X)(diphos)2], and imido complexes, [M(NH)(X)(diphos)2)]Y, (M = Mo, W) with diphosphine coligands (diphos = dppe/depe), various trans ligands (X = N3-, Cl-, NCCH3) and different counterions (Y-= Cl-, BPh4-) is investigated. These compounds are studied by infrared and Raman spectroscopies; they are also studied with isotope-substitution and optical-absorption, as well as emission, spectroscopies. In the nitrido complexes with trans-azido and -chloro coligands, the metal-N stretch is found at about 980 cm(-1); upon protonation, it is lowered to about 920 cm(-1). The 1A1 --> 1E (n --> pi) electronic transition is observed for [Mo(N)(N3)(depe)2] at 398 nm and shows a progression in the metal-N stretch of 810 cm(-1). The corresponding 3E --> 1A (pi --> n) emission band is observed at 542 nm, exhibiting a progression in the metal-N stretch of 980 cm(-1). In the imido system [Mo(NH)(N3)(depe)2]BPh4, the n --> pi transition is shifted to lower energy (518 nm) and markedly decreases in intensity. In the trans-nitrile complex [Mo(N)(NCCH3)(dppe)2]BPh4, the metal-N(nitrido) stretching frequency increases to 1016 cm(-1). The n --> pi transition now is found at 450 nm, shifting to 525 nm upon protonation. Most importantly, the reduction of this nitrido trans-nitrile complex is drastically facilitated compared to its counterparts with anionic trans-ligands (Epred = -1.5 V vs Fc+/Fc). On the other hand, the basicity of the nitrido group is decreased (pKa{[Mo(NH)(NCCH3)(dppe)2](BPh4)2} = 5). The implications of these findings with respect to the Chatt cycle are discussed.     

Directly observed reductive elimination of aryl halides from monomeric arylpalladium(II) halide complexes

Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3 to Pd[P(t-Bu)3](Ar)(X) (X = Cl, Br, I). Conditions to observe the equilibrium between reductive elimination and oxidative addition were established with five haloarenes. Reductive elimination of aryl chloride was most favored thermodynamically, and elimination of aryl iodide was the least favored. However, reductive elimination from the aryl chloride complex was the slowest, and reductive elimination from the aryl bromide complex was the fastest. These data show that the electronic properties of the halide, not the thermodynamic driving force for the addition of elimination reaction, control the rates for addition and elimination of haloarenes. Mechanistic data suggest that reversible reductive elimination of aryl bromide to form Pd[P(t-Bu)3] and free aryl bromide is followed by rate-limiting coordination of P(t-Bu)3 to form Pd[P(t-Bu)3]2.     

Ligand rotation in [Ar(R)N]3M-N2-M'[N(R)Ar]3(M, M' = MoIII, NbIII; R = iPr and tBu) dimers

Earlier calculations on the model N2-bridged dimer (micro-N2)-{Mo[NH2]3}2 revealed that ligand rotation away from a trigonal arrangement around the metal centres was energetically favourable resulting in a reversal of the singlet and triplet energies such that the singlet state was stabilized 13 kJ mol(-1) below the D(3d) triplet structure. These calculations, however, ignored the steric bulk of the amide ligands N(R)Ar (R =iPr and tBu, Ar = 3,5-C6H3Me2) which may prevent or limit the extent of ligand rotation. In order to investigate the consequences of steric crowding, density functional calculations using QM/MM techniques have been performed on the Mo(III)Mo(III) and Mo(III)Nb(III) intermediate dimer complexes (mu-N(2))-{Mo[N(R)Ar]3}2 and [Ar(R)N]3Mo-(mu-N2)-Nb[N(R)Ar]3 formed when three-coordinate Mo[N(R)Ar]3 and Nb[N(R)Ar]3 react with dinitrogen. The calculations indicate that ligand rotation away from a trigonal arrangement is energetically favourable for all of the ligands investigated and that the distortion is largely electronic in origin. However, the steric constraints of the bulky amide groups do play a role in determining the final orientation of the ligands, in particular, whether the ligands are rotated at one or both metal centres of the dimer. Analogous to the model system, QM/MM calculations predict a singlet ground state for the (mu-N2)-{Mo[N(R)Ar]3}2 dimers, a result which is seemingly at odds with the experimental triplet ground state found for the related (mu-N2)-{Mo[N(tBu)Ph]3}2 system. However, QM/MM calculations on the (mu-N2)-{Mo[N(tBu)Ph]3}2 dimer reveal that the singlet-triplet gap is nearly 20 kJ mol(-1) smaller and therefore this complex is expected to exhibit very different magnetic behaviour to the (mu-N2)-{Mo[N(R)Ar]3}2 system.     

Synthesis and structures of selected triazapentadienate of Li, Mn, Fe, Co, Ni, Cu(I), and Cu(II) using 2,4-N,N'-disubstituted 1,3,5-triazapentadienate anions as ancillary ligands: [N(Ar)C(NMe2)NC(NMe2)N(R)](-) (Ar = Ph, 2,6-(i)Pr2-C6H3; R = H, SiMe3)

Addition reaction of ArN(SiMe 3)M (Ar = Ph or 2,6 - (i) Pr 2-C 6H 3 (Dipp); M = Li or Na) to 2 equivalents of alpha-hydrogen-free nitrile RCN (R = dimethylamido) gave the dimeric [M{N(Ar)C(NMe 2)NC(NMe 2)N(SiMe 3)}] 2 ( 1a, Ar = Ph, M = Li; 1b, Ar = Ph, M = Na; 1c, Ar = Dipp, M = Li). 1d was obtained by hydrolysis of 1c at ambient temperature. Treatment of a double ratio of 1a or 1b with anhydrous MCl 2 (M = Mn, Fe, Co) yielded the 1,3,5-triazapentadienato complexes [M{N(Ph)C(NMe 2)NC(NMe 2)N(SiMe 3)} 2] (M = Mn, 2; Fe, 3; Co, 4) and with NiCl 2.6H 2O gave [M{N(Ph)C(NMe 2)NC(NMe 2)N(H)} 2] (M = Ni, 5). Treatment of an equiv of 1c with anhydrous CuCl in situ and in air led to complexes [{N(Dipp)C(NMe 2)NC(NMe 2)N(SiMe 3)}CuPPh 3] 6 and [Cu{N(Dipp)C(NMe 2)NC(NMe 2)N(H)} 2] 7, respectively. 1c, 1d, and 2- 7 were characterized by X-ray crystallography and microanalysis. 1c, 1d, 5, and 6 were well characterized by (1)H, (13)C NMR, 1c by (7)Li, and 6 by (31)P NMR as well. The structural features of these complexes were described in detail.