Daniel Tofan

Photochemical Incorporation of Diphosphorus Units into Organic Molecules

A niobium-based method for thermal transfer of P2 to 1,3dienes has been described previously, but this sole extant method is of limited preparative value due to the multi-step nature of the synthesis. In order to make the interesting class of bior tetracyclic P2R4 molecules readily available for detailed scrutiny, we sought and have now discovered a simple one-step procedure, reported herein. The method consists of P4 photolysis in the presence of commercially available 1,3diene molecules to produce directly the diphosphane target molecules. In 1937, Rathenau reported that the conversion of white phosphorus to red phosphorus under UV irradiation using a mercury lamp involves unimolecular dissociation of P4 into P2 molecules, followed by recombination of the latter into red phosphorus. In one report on the P4 cophotolysis with metal carbonyl complexes, Dahl et al. mention that “P4 in solution photolyzes readily to P2 at ambient temperatures”. [3] There have been several other reports on the co-photolysis of P4 with metal carbonyl complexes and generation of metal– phosphorus products, yet we have not found any reports on using photolysis of P4 molecules for the direct inclusion of phosphorus atoms into organic substrates. Electronic absorption features for P4 in the gas phase at 62 8C have been reported in the UV region below 300 nm. We found that upon using a mercury lamp that irradiates predominantly at 254 nm, the photolysis of P4 in the presence of 1,3-dienes affords products consistent with double Diels– Alder additions of diene molecules to P2 units. Initial experiments focused on generating the previously reported tetracyclic diphosphane C12H16P2 by irradiating a mixture of P4 and 1,3-cyclohexadiene (CHD). The appearance of the characteristic sharp singlet of the targeted diphosphane product at d = 80 ppm in P NMR spectra of crude product mixtures was encouraging. However, upon attempting to quantify and isolate the desired diphosphane, only quantities on the order of several milligrams were obtained. Nevertheless, when 1,3-cyclohexadiene was replaced with conjugated dienes that are more transparent in the window of P4 absorption, improved results were obtained. The photolysis of hexane solutions containing P4 and 2,3dimethyl-1,3-butadiene (DMB) in slight excess, led to the appearance of a singlet in the P NMR spectra at d = 53.8 ppm, consistent with formation of the desired Diels– Alder cycloaddition product 3,4,8,9-tetramethyl-1,6diphosphabicyclo(4.4.0)deca-3,8-diene (1, C12H20P2, Scheme 1 and Figure 1). This molecule has only been prepared and reported previously as a ligand in a complex with tungsten pentacarbonyl, and it is closely related to the mixed-pnictogen ligand in the complex [(C12H20PAs)W(CO)5]. [8]

Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

Tetrahedral [MoO4]2− readily binds CO2 at room temperature to produce a robust monocarbonate complex, [MoO3(κ2-CO3)]2−, that does not release CO2 even at modestly elevated temperatures (up to 56 °C in solution and 70 °C in the solid state). In the presence of excess carbon dioxide, a second molecule of CO2 binds to afford a pseudo-octahedral dioxo dicarbonate complex, [MoO2(κ2-CO3)2]2−, the first structurally characterized transition-metal dicarbonate complex derived from CO2. The monocarbonate [MoO3(κ2-CO3)]2− reacts with triethylsilane in acetonitrile under an atmosphere of CO2 to produce formate (69% isolated yield) together with silylated molybdate (quantitative conversion to [MoO3(OSiEt3)]−, 50% isolated yield) after 22 hours at 85 °C. This system thus illustrates both the reversible binding of CO2 by a simple transition-metal oxoanion and the ability of the latter molecular metal oxide to facilitate chemical CO2 reduction.

Thermodynamic and Kinetic Study of Cleavage of the N–O Bond of N-Oxides by a Vanadium(III) Complex: Enhanced Oxygen Atom Transfer Reaction Rates for Adducts of Nitrous Oxide and Mesityl Nitrile Oxide

Thermodynamic, kinetic, and computational studies are reported for oxygen atom transfer (OAT) to the complex V(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2, 1) from compounds containing N-O bonds with a range of BDEs spanning nearly 100 kcal mol(-1): PhNO (108) > SIPr/MesCNO (75) > PyO (63) > IPr/N2O (62) > MesCNO (53) > N2O (40) > dbabhNO (10) (Mes = mesityl; SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene; Py = pyridine; IPr = 1,3-bis(diisopropyl)phenylimidazol-2-ylidene; dbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene). Stopped flow kinetic studies of the OAT reactions show a range of kinetic behavior influenced by both the mode and strength of coordination of the O donor and its ease of atom transfer. Four categories of kinetic behavior are observed depending upon the magnitudes of the rate constants involved: (I) dinuclear OAT following an overall third order rate law (N2O); (II) formation of stable oxidant-bound complexes followed by OAT in a separate step (PyO and PhNO); (III) transient formation and decay of metastable oxidant-bound intermediates on the same time scale as OAT (SIPr/MesCNO and IPr/N2O); (IV) steady-state kinetics in which no detectable intermediates are observed (dbabhNO and MesCNO). Thermochemical studies of OAT to 1 show that the V-O bond in O≡V(N[t-Bu]Ar)3 is strong (BDE = 154 ± 3 kcal mol(-1)) compared with all the N-O bonds cleaved. In contrast, measurement of the N-O bond in dbabhNO show it to be especially weak (BDE = 10 ± 3 kcal mol(-1)) and that dissociation of dbabhNO to anthracene, N2, and a (3)O atom is thermodynamically favorable at room temperature. Comparison of the OAT of adducts of N2O and MesCNO to the bulky complex 1 show a faster rate than in the case of free N2O or MesCNO despite increased steric hindrance of the adducts.

White phosphorus activation at a metal-phosphorus triple bond: a new route to cyclo-triphosphorus or cyclo-pentaphosphorus complexes of niobium.

The Nb-P triple bond in [P≡Nb(N[Np]Ar)(3)](-) (Np = CH(2)(t)Bu; Ar = 3,5-Me(2)C(6)H(3)) has produced the first case of P(4) activation by a metal-ligand multiple bond. Treatment of P(4) with the sodium salt of the niobium phosphide complex in weakly coordinating solvents led to formation of the cyclo-P(3) anion [(P(3))Nb(N[Np]Ar)(3)](-). Treatment in tetrahydrofuran (THF) led to the formation of a cyclo-P(5) anion [(Ar[Np]N)(η(4)-P(5))Nb(N[Np]Ar)(2)](-), which represents a rare example of a substituted pentaphosphacyclopentadienyl ligand. The P(4) activation pathway was shown to depend on the dimer-monomer equilibrium of the niobium phosphide reagent, which, in turn, depends on the solvent used for the reaction. The pathway leading to the cyclo-P(3) product was shown to require a 2:1 ratio of the phosphide anion to P(4), while the cyclo-P(5) formation requires a 1:1 ratio. The cyclo-P(3) salt has been isolated in 56% yield as orange crystals of the [Na(THF)](2)[(P(3))Nb(N[Np]Ar)(3)](2) dimer or in 83% yield as an orange powder of [Na(12-crown-4)(2)][(P(3))Nb(N[Np]Ar)(3)]. A solid-state X-ray diffraction experiment on the former salt revealed that each Nb-P(3) unit exhibits pseudo-C(3) symmetry, while (31)P NMR spectroscopy showed a sharp signal at -223 ppm that splits into a doublet-triplet pair below -50 °C. It was demonstrated that this salt can serve as a P(3)(3-) source upon treatment with AsCl(3), albeit with modest yield of AsP(3). The cyclo-P(5) salt was isolated in 71% yield and structurally characterized from red crystals of [Na(THF)(6)][(Ar[Np]N)(η(4)-P(5))Nb(N[Np]Ar)(2)]. The anion in this salt can be interpreted as the product of trapping of an intermediate pentaphosphacycplopentadienyl structure through migration of one anilide ligand onto the P(5) ring. The W(CO)(5)-capped cyclo-P(3) salt was also isolated in 60% yield as [Na(THF)][(OC)(5)W(P(3))Nb(N[Np]Ar)(3)] from the activation of 0.5 equiv of P(4) with the sodium salt of the tungsten pentacarbonyl adduct of the niobium phosphide anion.

Bicyclic dinuclear tris-(ditopic diphosphane) complexes of zerovalent group 10 metals

Selective formation of bimetallic group 10 complexes using the Cs symmetric, bicyclic diphosphane P2C12H20 is reported herein. With its eclipsed lone pairs disposed at a relative angle of ca. 45°, the diphosphane framework is ideally suited to form multiple bridges between two metal centers. The complexes contain {M2P6} cages with three diphosphane bridges and a pair of trans-axial ligands such as EPh3 (E = P, As, Sb) or η1-P2C12H20. X-Ray crystallography experiments revealed that the cages have a pseudo-D3h symmetry, with metal–metal distances in the 3.9–4.1 A range. The complexes were isolated in 48–91% yield as crystalline, bright yellow or orange powders. Substitution of the axial ligands with the {M2P6} cages remaining intact was also observed.

Two-Step Binding of O2 to a Vanadium(III) Trisanilide Complex To Form a Non-Vanadyl Vanadium(V) Peroxo Complex

Treatment of V(N[(t)Bu]Ar)(3) (1) (Ar = 3,5-Me(2)C(6)H(3)) with O(2) was shown by stopped-flow kinetic studies to result in the rapid formation of (η(1)-O(2))V(N[(t)Bu]Ar)(3) (2) (ΔH(‡) = 3.3 ± 0.2 kcal/mol and ΔS(‡) = -22 ± 1 cal mol(-1) K(-1)), which subsequently isomerizes to (η(2)-O(2))V(N[(t)Bu]Ar)(3) (3) (ΔH(‡) = 10.3 ± 0.9 kcal/mol and ΔS(‡) = -6 ± 4 cal mol(-1) K(-1)). The enthalpy of binding of O(2) to form 3 is -75.0 ± 2.0 kcal/mol, as measured by solution calorimetry. The reaction of 3 and 1 to form 2 equiv of O≡V(N[(t)Bu]Ar)(3) (4) occurs by initial isomerization of 3 to 2. The results of computational studies of this rearrangement (ΔH = 4.2 kcal/mol; ΔH(‡) = 16 kcal/mol) are in accord with experimental data (ΔH = 4 ± 3 kcal/mol; ΔH(‡) = 14 ± 3 kcal/mol). With the aim of suppressing the formation of 4, the reaction of O(2) with 1 in the presence of (t)BuCN was studied. At -45 °C, the principal products of this reaction are 3 and (t)BuC(═O)N≡V(N[(t)Bu]Ar)(3) (5), in which the bound nitrile has been oxidized. Crystal structures of 3 and 5 are reported.

Synthesis and Characterization of Iron Derivatives Having a Pyridine-Linked Bis(anilide) Pincer Ligand

A pyridine-linked bis(aniline) pincer ligand, [2]H(2) ([2]H(2) = (2,6-NC(5)H(3)(2-(2,4,6-Me(3)C(6)H(2))-NHC(6)H(4))(2)), has been synthesized in two steps. Deprotonation with Me(3)SiCH(2)Li followed by metalation with FeCl(2) yielded a LiCl adduct of [2]Fe. The complex is freed of LiCl with excess TlPF(6) or by crystallization from toluene/petroleum ether, giving [2]Fe(THF). [2]Fe(THF) reacts with I(2) and O(2) to generate [2]FeI and ([2]Fe)(2)O, respectively. The complexes have been characterized by (1)H NMR spectroscopy, elemental analysis, X-ray crystallography, and UV-vis spectroscopy. [2]Fe(THF) has been examined using cyclic voltammetry.

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

The 3,4,8,9-tetramethyl-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P2(C6H10)2) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P-P bonded λ(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSbPh3 has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)2 (87%), O2P2(C6H10)2 (94%), SP2(C6H10)2 (56%), and S2P2(C6H10)2 (87%). Computational studies indicate that the oxygen-atom transfer reactions involve penta-coordinated phosphorus intermediates that have four-membered {PONC} cycles. The P-E bond dissociation enthalpies in EP2(C6H10)2 were measured via calorimetric studies to be 134.7 ± 2.1 kcal/mol for P-O, and 93 ± 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P-P bond and formation of diphosphinate O3P2(C6H10)2 was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P2(C6H10)2(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P2(C6H10)2 (91% for R = Mes). Metalation reactions with the bulky diiminodiphosphorane ligand (MesN)2P2(C6H10)2 (nppn) allowed for the isolation and characterization of (nppn)Mo(η(3)-C3H5)Cl(CO)2 (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(η(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO2/ethylene coupling

A family of cis-macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene, or P2(dmb)2, produced phosphino-phosphonium salts [R-P2(dmb)2]X, where R is methyl, benzyl and isobutyl, in yields of 90–96%. Treatment of these salts with organolithium or Grignard reagents yielded symmetric and unsymmetric macrocyclic diphosphines of the form cis-1-R-6-R′-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R′-DPC, in which R′ is methyl, cyclohexyl, phenyl or mesityl, in yields of 46–94%. Alternatively, symmetric diphosphine Cy2-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl2P2(dmb)2. As a first application, these cis-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO2 and ethylene, for which they showed promising catalytic activity.