Synthesis of Al complexes containing phenoxy-imine ligands and their use as the catalyst precursors for efficient living ring-opening polymerisation of epsilon-caprolactone

Al complexes containing phenoxy-imine ligands of type, Me2Al[O-2-R1-6-(R2N=CH)C6H3] [R1 = Me, R2 = 2,6-iPr2C6H3 (1a), tBu (1b); R1 = tBu, R2 = 2,6-iPr2C6H3 (2a), tBu (2b), cyclohexyl (2c), adamantyl (2d), C6H5 (2e), 2,6-Me2C6H3 (2f), C6F5 (2g)] have been prepared in high yields from AlMe3 by treating with 1.0 equiv. of 2-R1-6-(R2N=CH)C6H3OH in n-hexane. Structures for 1a, 1b, 2a-e and 2g were determined by X-ray crystallography, and these complexes have a distorted tetrahedral geometry around Al; both the Al-O and the Al-N bond distances were influenced by substituents in both the aryloxo and the imino groups. Me2Al[mu2-O-2-(R2N=CH)C6H4](AlMe3) [R2 = 2,6-iPr2C6H3 (3a), tBu (3b)] were prepared exclusively by reaction of AlMe3 with 2-(R2N=CH)C6H4OH, and these complexes form a distorted tetrahedral geometry around each Al centre with additional AlMe3 coordinating to the oxygen in the phenoxy-imine ligand. Complexes 1a, 1b and 2a-g were tested as catalyst precursors for ring-opening polymerisation (ROP) of epsilon-caprolactone (CL) in the presence of (n)BuOH (1.0 equiv. to Al), and their catalytic activities were strongly influenced by the imino substituent (R2). The efficient ROP has been achieved using the C6F5 analogue (2g), with the ROP taking place in a living manner.     

Simple syntheses, structural diversity, and Tishchenko reaction catalysis of neutral homoleptic rare earth(II or III) 3,5-di-tert-butylpyrazolates--the structures of

The homoleptic rare-earth pyrazolate complexes [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln = La, Nd, Sm, Lu), [Eu4(tBu2pz)8] and the mixed oxidation state species [Yb2(tBu2pz)5] (tBu2pz = 3,5-di-tert-butylpyrazolate) have been prepared by a simple reaction between the corresponding rare-earth metal and 3,5-di-tert-butylpyrazole, in the presence of mercury, at elevated temperatures. In addition, [Yb2(tBu2pz)6] was prepared by redox transmetallation/ligand exchange between ytterbium, diphenylmercury(II) and tBu2pzH in toluene, whilst the same reactants in toluene under different conditions or in diethyl ether gave [Yb2(tBu2pz)5]. The complexes of the trivalent lanthanoids display dimeric structures [Ln2(tBu2pz)6] (Ln = La, Nd, Yb, Lu) with chelating eta2-terminal and eta2:eta2-bridging pyrazolate coordination. The considerably smaller Sc3+ ion forms monomeric [Sc(tBu2pz)3] of putative D3h molecular symmetry, with pyrazolate ligands solely eta2-bonded. [Eu4(tBu2pz)8] is a structurally remarkable tetranuclear EuII complex with two types of europium centres in a linear array. The outer two are bonded to one terminal and two bridging pyrazolates, and the inner two are coordinated by four bridging ligands. Unprecedented mu-eta5:eta2 pyrazolate ligation is observed, with each outer Eu2+ sandwiched between two eta5-bonded pyrazolate groups, which are also eta2-linked to an inner Eu2+. The two inner Eu2+ ions are linked together by two equally occupied components of each of two symmetry related, disordered pyrazolate groups with one component eta4:eta2 bridging and one eta3:eta2 bridging. [La2(tBu2pz)6] has also been shown to be a Tishchenko reaction catalyst with several organic substrates.     

Crystal retro-engineering: structural impact on silver(I) complexes with changing complexity of tris(pyrazolyl)methane ligands

The preparation and structures of seven new silver(I) complexes involving the parent tris(pyrazolyl)methane unit, [C(pz)(3)], as the donor set, {[C6H5CH2OCH2C(pz)3]Ag}(BF4), {[C6H5CH2OCH2C(pz)3]2Ag3}(CF3SO3)3, {[HOCH2C(pz)3]Ag}(BF4), {[HOCH2C(pz)3]Ag}(CF3SO3), {[HC(pz)3]2Ag2(CH3CN)}(BF4)2, {[HC(pz)3]Ag}(PF6), and {[HC(pz)3]Ag}(CF3SO3), are reported. This project is based on a retro-design of our multitopic C6H(6-n)[CH2OCH2C(pz)3]n (pz = pyrazolyl ring, n = 2, 3, 4, and 6) family of ligands in such a way that each new ligand has one fewer organizational feature. The kappa2-kappa1 bonding mode of the [C(pz)3] units to two silvers, also observed with the multitopic ligands, is the dominant structural feature in all cases. Changing the counterion has important effects on the local structures and on crystal packing. When these structures are compared to similar ones based on the multitopic C6H(6-n)[CH2OCH2C(pz)3]n ligands, it has been shown that the presence of the rigid parts (central arene core and the [C(pz)3] units) are important in order to observe highly organized supramolecular structures. The presence of the flexible ether linkage is also crucial, allowing all noncovalent forces to manifest themselves in a cumulative and complementary manner.     

Structural comparisons of silver(I) complexes of third-generation ligands built from tridentate (o-C(6)H(4)[CH(2)OCH(2)C(pz)(3)](2)) versus bidentate poly(1-pyrazolyl)methane units (o-C(6)H(4)[CH(2)OCH(2)CH(pz)(2)](2)) (pz = pyrazolyl ring)

The new bitopic, bis(1-pyrazolyl)methane-based ligand o-C6H4[CH2OCH2CH(pz)2]2 (L2, pz = pyrazolyl ring) is prepared from the reaction of (pz)2CHCH2OH (obtained from the reduction of (pz)2CHCOOH with BH3.S(CH3)2) with NaH, followed by the addition of alpha,alpha'-dibromo-o-xylene. The reaction of L2 with AgPF6 or AgO3SCF3 yields {o-C6H4[CH2OCH2CH(pz)2]2(AgPF6)}n or {o-C6H4[CH2OCH2CH(pz)2]2(AgO3SCF3)}n, respectively. Both compounds in the solid state have tetrahedral silver(I) centers arranged in a 1D coordination polymer network. The analogous ligand based on tris(1-pyrazolyl)methane units, o-C6H4[CH2OCH2C(pz)3]2 (L3), reacts with AgO3SCF3 to form a similar coordination polymer, {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)}n. In this case, each tris(pyrazolyl)methane unit in L3 adopts the kappa2-kappa0 bonding mode. Crystallization of a 3:1 mixture of AgO3SCF3 and L3 yields {o-C6H4[CH2OCH2C(pz)3]2(AgO3SCF3)2}n, in which the tris(1-pyrazolyl)methane units adopt a kappa2-kappa1 coordination mode.     

Halide and nitrite recognizing hexanuclear metallacycle copper(II) pyrazolates

Halide-centered hexanuclear, anionic copper(II) pyrazolate complexes [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)X](-), X = Cl, Br, I are isolated in a good yield from the redox reaction of the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] with a halide source such as PPh(3)AuCl or [Bu(4)N]X, X = Cl, Br, or I, in air. X-ray structures of the anion-centered hexanuclear complexes show that the six copper atoms are bridged by bis(3,5-trifluoromethyl)pyrazolate and hydroxyl ligands above and below the six copper atom plane. The anions are located at the center of the cavity and weakly bound to the six copper atoms in a μ(6)-arrangement, Cu-X = ~3.1 ?. A nitrite-centered hexanuclear copper(II) pyrazolate complex [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))](-) was obtained when a solution of [PPN]NO(2) in CH(3)CN was added dropwise to the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] dissolved in CH(3)CN, in air. Blue crystals are produced by slow evaporation of the acetonitrile solvent. The X-ray structure of [PPN][trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))] complex shows the nitrite anion sits in the hexanuclear cavity and is perpendicular to the copper plane with a O-N-O angle of 118.3(7)°. The (19)F and (1)H NMR of the pyrazolate ring atoms are sensitive to the anion present in the ring. Anion exchange of the NO(2)(-) by Cl(-) can be observed easily by (1)H NMR.     

Structures and solvatochromic phosphorescence of dicationic terpyridyl-platinum(II) complexes with foldable oligo(ortho-phenyleneethynylene) bridging ligands

A series of binuclear organoplatinum(II) complexes, [(tBu3tpy)Pt--(C[triple chemical bond]C--1,2-C6H4)n--C[triple chemical bond]C--Pt(tBu3tpy)][ClO4]2 (1-7, n=1, 2, 3, 4, 5, 6, 8; tBu3tpy=4,4',4'-tri-tert-butyl-2,2':6',2'-terpyridine) with foldable oligo(ortho-phenyleneethynylene) linkers were prepared and characterized by spectroscopic methods and/or X-ray crystallographic analyses. In the crystal structures of 32.5 CH3OH, 5CH3CN, and 64 CH3CN, each of the bridging ortho-phenyleneethynylene ligands has a partially folded conformation. In aerated water/acetonitrile mixtures with water percentages larger than 40 %, the emission of complexes 3-7 are red-shifted and enhanced when compared to those recorded in acetonitrile. The red-shift in emission energy and enhanced emission intensity can be attributed to the inter- and/or intramolecular interactions induced by the addition of water to solutions of the platinum(II) complexes in acetonitrile. Data from dynamic light scattering and transmission electron microscopy studies revealed that these binuclear platinum(II) complexes aggregated into nanosized particles in acetonitrile/water mixtures. Hydrophobic folding of the ortho-phenyleneethynylene linkers in acetonitrile/water mixtures is postulated.     

Formation of P-C bonds under unexpectedly mild conditions. Phosphoryl migration and metal coordination of diphenylphosphinomethyl-oxazolines and -thiazolines

The heterocycles 2-methyl-2-oxazoline (mox) and 2-methyl-2-thiazoline (mth) react with Ph2PCl under mild conditions, in the presence of NEt3 which promotes their phosphorylation by stabilization of their enamino tautomers mox(e) and mth(e), respectively, and which also behaves as HCl scavenger. Depending on the reaction conditions, three different phosphine ligands were obtained in good yields from mox: the monophosphine Ph2PCH2C=NCH2CH2O (1ox) and the isomeric diphosphines Ph2PCH=COCH2CH2NPPh2 (2ox) (X-ray structure) and (Ph2P)2CHC=NCH2CH2O (3ox). The formation of these ligands involves phosphoryl migration reactions, which were studied by NMR spectroscopy. The synthesis and the X-ray structures of the corresponding diphenylphosphinothiazolines Ph2PCH2C=NCH2CH2S (1th) and Ph2CH=CSCH2CH2NPPh2 (2th) are also reported but the thiazoline analog of the geminal diphosphine 3ox was not observed. The metal complexes [Pt(3ox-H)2] x 4 CH2Cl2 (4 x 4 CH2Cl2), [Pt(Me)I(1ox)] (5), [Pt(Me)2(1ox)] (7), [Pd(dmba-C,N)(1th)]OTf x 0.25 Et2O (8 x 0.25 Et2O), [Pd(dmba-C,N)(1th-H)] (9), and [9 x {Pd(dmba-C,N)Cl}] x 2.5 C6H6 (10 x 2.5 C6H6) have been prepared and structurally characterized by X-ray diffraction.     

Synthesis and structural characterization of configurational isomers of tungsten-palladium complexes with bridging diphenyl(dithioalkoxycarbonyl)phosphine as a ligand and phosphine transfer from tungsten to palladium

Treatment of the complex [W(CO)5[PPh2(CS2Me)]] (2) with [Pd(PPh3)4] (1) affords binuclear complexes such as anti-[(Ph3P)2Pd[mu-eta 1,eta 2-(CS2Me)PPh2]W(CO)5] (3), syn-[(Ph3P)2Pd[mu-eta 1,eta 2-(CS2Me)PPh2]W(CO)5] (4), and trans-[W(CO)4(PPh3)2] (5). In 3 and 4, respectively, the W and Pd atoms are in anti and syn configurations with respect to the P-CS2 bond of the diphenyl(dithiomethoxycarbonyl)phosphine ligand, PPh2(CS2Me). Complex 3 undergoes extensive rearrangement in CHCl3 at room temperature by transfer of a PPh3 ligand from Pd to W, eliminating [W(CO)5(PPh3)] (7), while the PPh2CS2Me ligand transfers from W to Pd to give [[(Ph3P)Pd[mu-eta 1,eta 2-(CS2Me)PPh2]]2] (6). In complex 6, the [Pd(PPh3)] fragments are held together by two bridging PPh2(CS2Me) ligands. Each PPh2(CS2Me) ligand is pi-bonded to one Pd atom through the C=S linkage and sigma-bonded to the other Pd through the phosphorus atom, resulting in a six-membered ring. Treatment of Pd(PPh3)4 with [W(CO)5[PPh2[CS2(CH2)nCN]]] (n = 1, 8a; n = 2, 8b) in CH2Cl2 affords syn-[(Ph3P)2Pd[mu-eta 1,eta 2-[CS2(CH2)nCN]PPh2]W(CO)5] (n = 1, 9a; n = 2, 9b). Similar configurational products syn-[(Ph3P)2Pd[mu-eta 1,eta 2-(CS2R)PPh2]W(CO)5] (R = C2H5, C3H5, C2H4OH, C3H6CN, 11a-d) are synthesized by the reaction of Pd(PPh3)4 with [W(CO)5[PPh2(CS2R)]] (R = C2H5, C3H5, C2H4OH, C3H6CN, 10a-d). Although complexes 11a-d have the same configuration as 9a,b, the SR group is oriented away from Pd in the former and near Pd in the latter. In these complexes, the diphenyl(dithioalkoxycarbonyl)phosphine ligand is bound to the two metals through the C=S pi-bonding and to phosphorus through the sigma-bonding. All of the complexes are identified by spectroscopic methods, and the structures of complexes 3, 6, 9a, and 11d are determined by single-crystal X-ray diffraction. Complexes 3, 9, and 11d crystallize in the triclinic space group P1 with Z = 2, whereas 6 belongs to the monoclinic space group P2/c with Z = 4. The cell dimensions are as follows: for 3, a = 10.920(3) A, b = 14.707(5) A, c = 16.654(5) A, alpha = 99.98(3) degrees, beta = 93.75(3) degrees, gamma = 99.44(3) degrees; for 6, a = 15.106(3) A, b = 9.848(3) A, c = 20.528(4) A, beta = 104.85(2) degrees; for 9a, a = 11.125(3) A, b = 14.089(4) A, c = 17.947(7) A, alpha = 80.13(3) degrees, beta = 80.39(3) degrees, gamma = 89.76(2) degrees; for 11d, a = 11.692(3) A, b = 13.602(9) A, c = 18.471(10) A, alpha = 81.29(5) degrees, beta = 80.88(3) degrees, gamma = 88.82(1) degrees.     

Small scorpionate ligands: silver(I)-organophosphane complexes of 5-CF(3)-substituted scorpionate ligand combining a B-H...Ag coordination motif

The first 5-substituted trihydro(azolyl)borate system, the sodium trihydro(5-CF3-pyrazol-1-yl)borate, Na[H3B(5-(CF3)pz)], has been synthesized by the reaction of 3-trifuoromethyl-pyrazole with NaBH4 in high yield. Na[H3B(5-(CF3)pz)] reacts with AgNO3 in the presence of monodentate tertiary phosphanes PR3 (PR3=P(C6H5)3, P(p-C6H4CH3)3, P(m-C6H4CH3)3, P(o-C6H4CH3)3, or PCH3(C6H5)2) to afford silver(I) bis(phosphane) adducts. These compounds have been characterized by elemental analyses, FTIR, ESI-MS, and multinuclear (1H, 19F, and 31P) NMR spectroscopy. Solid-state structures of {[H3B(5-(CF3)pz)]Ag[P(C6H5)3]2} and {[H3B(5-(CF3)pz)]Ag[P(p-C6H4CH3)3]2} are also reported. They feature kappa2-N,H-bonded trihydro(pyrazolyl)borate ligands and pseudo-tetrahedral silver atoms.     

Mononuclear, helical binuclear palladium and lithium complexes bearing a new pyrrole-based NNN-pincer ligand: fluxional property

A new pyrrole based NNN-pincer ligand, 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2, was readily synthesized in two steps from pyrrole in 56% yield. The lithiation of the pincer ligand 2 using n-BuLi led to isolation of the dimeric lithium complex, [Li{μ-C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}](2) 4, in 23% crystalline yield. The transmetalation reaction of 4 with [Pd(PhCN)(2)Cl(2)] afforded the mononuclear Pd(II) complex, [PdCl{C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}] 5, containing one chloride ion in 45% yield. Alternatively 5 was obtained in an excellent yield of 87% by the reaction 2 of with [Pd(COD)Cl(2)] in the presence of triethylamine. On the contrary, a 20-membered macrometalacyclic molecule, [Pd(2)Cl(4){μ-C(4)H(3)N-2,5-(CH(2)Me(2)pz)(2)-N,N}(2)] 6, in which two PdCl(2) units are bridged by two molecules of 2 to give a helical structure, was synthesized by the reaction of 2 with [Pd(COD)Cl(2)] in the absence of base. The acetate analogue of complex 5, [Pd(OAc){C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}] 3, was obtained by the treatment of 2 with [Pd(OAc)(2)]. The pyrrole twist angle of 5 is higher than that of 3. Complexes 3 and 5 show an AB pattern for their methylene protons at room temperature in CDCl(3) as well as in DMSO-d(6). The variable temperature NMR studies showed that the acetate and chloride complexes exhibit slightly different coalescence temperatures, which is a solvent dependent phenomenon, and twist angles.     

Synthesis and structural characterization of unprecedented bis-asymmetric heteroscorpionate U(III) complexes: [U(kappa3-H2B(pztBu,Me)(pzMe,tBu))2I] and [U(kappa3-H2B(pztBu,Me)(pzMe2))2I

[UI(3)(THF)(4)] reacts at room temperature with 2 equiv of KBp(tBu,Me), in toluene, yielding [U(kappa(3)-H(mu-H)B(pz(tBu,Me))(pz(Me,tBu)))(2)I] (1). This unprecedented complex, stabilized by two asymmetric heteroscorpionate ligands, is formed due to an isomerization process promoted in situ by the metal center. To find a general method for preparing this type of compound, we synthesized the novel asymmetric K[H(2)B(pz(tBu,Me))(pz(Me2))], and by a straightforward salt metathesis with [UI(3)(THF)(4)] the novel bis-asymmetric complex [U(kappa(3)-H(mu-H)B(pz(tBu,Me))(pz(Me2)))(2)I] (2) was isolated and characterized in the solid state and in solution. As indicated by X-ray crystallographic analysis, the U(III) in 1 and 2 is seven-coordinated by two tridentate asymmetric dihydrobis(pyrazoly)borates and by an iodide. In both cases, the coordination geometry around the metal is very distorted, the pentagonal bipyramid being the one which better describes the arrangement of the atoms around the U(III). An approximate C(2) axis can be defined in the solid state, and is maintained in solution as indicated by the (1)H NMR spectrum of 1 and 2. In the course of attempting to crystallize some of the compounds, monocrystals of the dimer [U(kappa(3)-Bp(tBu,Me))(Hpz(tBu,Me))I(mu-I)](2) (3) were isolated. In this compound each U(III) atom is seven-coordinated by one kappa(3)-Bp(tBu,Me), by one terminal and by two bridging iodide ligands, and by a monodentate Hpz(tBu,Me), exhibiting a distorted 4:3 tetragonal base-trigonal geometry.     

Experimental and DFT study of the tautomeric behavior of cobalt-containing secondary phosphine oxides

New cobalt-containing secondary phosphine oxides [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4){mu,eta-PhC[triple chemical bond]CP(==O)(H)(R)}] (8 a: R=tBu; 8 b: R=Ph) were prepared by reaction of secondary phosphine oxides PhC[triple chemical bond]CP- (==O)(H)(R) (6 a: R=tBu; 6 b: R=Ph) with dppm-bridged dicobalt complex [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(6)] (2). The molecular structures of 8 a and 8 b were determined by single-crystal X-ray diffraction. Although palladium-catalyzed Heck reactions employing 8 b as ligand gave satisfying results, 8 a performed poorly in the same reaction. Judging from these results, a tautomeric equilibrium between 8 b and its isomeric form [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4){mu,eta-PhC[triple chemical bond]CP(OH)(Ph)}] 8 b' indeed takes place, but it is unlikely between 8 a and [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4){mu,eta-PhC[triple chemical bond]CP(OH)(tBu)}] (8 a'). The DFT studies demonstrated that reasonable activation energies for the tautomeric conversions can be achieved only via a bimolecular pathway. Since a tBu group is much larger than a Ph group, the conversion is presumably only feasible in the case of 8 bright harpoon over left harpoon8 b', but not in the case of 8 aright harpoon over left harpoon8 a'. Another cobalt-containing phosphine, namely, [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4){mu,eta-PhC[triple chemical bond]CP(NEt(2))(tBu)}] (7 a), and its oxidation product [(mu-PPh(2)CH(2)PPh(2))Co(2)(CO)(4){mu,eta-PhC[triple chemical bond]CP(==O)(NEt(2))(tBu)}] 7 a' were prepared from the reaction of PhC[triple chemical bond]CP(NEt(2))(tBu) (5 a) with 2. The molecular structures of 7 a and 7 a' were determined by single-crystal X-ray diffraction. The phosphorus atom is surrounded by substituents in a tetrahedral environment. A P--N single bond (1.676(3) A) is observed in the molecular structure of 7 a. Heck reactions employing 7 a/Pd(OAc)(2) as catalyst system exhibited efficiency comparable to that of 8 a/Pd(OAc)(2).     

Structural variation, dynamics, and catalytic application of palladium(II) complexes of di-N-heterocyclic carbene-amine ligands

A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))PdCl(2)] (12) and [trans-(kappa(2)-(Mes)CN(H)C(Mes))PdCl(2)] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C(s) symmetry and for 13 rotation of the mesityl groups is prevented. In the related C(1) complex [(kappa(3)-(tBu)CN(H)C(tBu))PdCl][Cl] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12-14 and two equivalents of AgBF(4) in acetonitrile gives the analogous complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))Pd(MeCN)(2)][BF(4)](2) (15), [trans-(kappa(2)-(Mes)CN(H)C(Mes))Pd(MeCN)(2)][BF(4)](2) (16) and [(kappa(3)-(tBu)CN(H)C(tBu))Pd(MeCN)][BF(4)](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors (tBu)C(H)N(Bn)C(H)(tBu)][Cl](2) (2) and [(tBu)C(H)N(H)C(H)(tBu)][BPh(4)](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively.     

A para-hydrogen investigation of palladium-catalyzed alkyne hydrogenation

The complexes [Pd(bcope)(OTf)2] (1a), where bcope is (C8H14)PCH2-CH2P(C8H14), and [Pd(tbucope)(OTf)2] (1b), where tbucope is (C8H14)PC6H4CH2P(tBu)2, catalyze the conversion of diphenylacetylene to cis- and trans-stilbene and 1,2-diphenylethane. When this reaction was studied with para-hydrogen, the characterization of [Pd(bcope)(CHPhCH2Ph)](OTf) (2a) and [Pd(tbucope)(CHPhCH2Ph)](OTf) (2b) was achieved. Magnetization transfer from the alpha-H of the CHPhCH2Ph ligands in these species proceeds into trans-stilbene. This process has a rate constant of 0.53 s-1 at 300 K in methanol-d4 for 2a, where DeltaH = 42 +/- 9 kJ mol-1 and DeltaS = -107 +/- 31 J mol-1 K-1, but in CD2Cl2 the corresponding rate constant is 0.18 s-1, with DeltaH = 79 +/- 7 kJ mol-1 and DeltaS = 5 +/- 24 J mol-1 K-1. The analogous process for 2b was too fast to monitor in methanol, but in CD2Cl2 the rate constant for trans-stilbene formation is 1.04 s-1 at 300 K, with DeltaH = 94 +/- 6 kJ mol-1 and DeltaS = 69 +/- 22 J mol-1 K-1. Magnetization transfer from one of the two inequivalent beta-H sites of the CHPhCH2Ph moiety proceeds into trans-stilbene, while the other site shows transfer into H2 or, to a lesser extent, cis-stilbene in CD2Cl2, but in methanol it proceeds into the vinyl cations [Pd(bcope)(CPh=CHPh)(MeOD)](OTf) (3a) and [Pd(tbucope)(CPh=CHPh)(MeOD)](OTf) (3b). When the same magnetization transfer processes are monitored for 1a in methanol-d4 containing 5 microL of pyridine, transfer into trans-stilbene is observed for two sites of the alkyl, but the third proton now becomes a hydride ligand in [Pd(bcope)(H)(pyridine)](OTf) (5a) or a vinyl proton in [Pd(bcope)(CPh=CHPh)(pyridine)](OTf) (4a). For 1b, under the same conditions, two isomers of [Pd(tbucope)(H)(pyridine)](OTf) (5b and 5b') and the neutral dihydride [Pd(tbucope)(H)2] (7) are detected. The single vinylic CH proton in 3 and the hydride ligands in 4 and 5 appear as strong emission signals in the corresponding 1H NMR spectra.     

Neutral and zwitterionic low-coordinate titanium complexes bearing the terminal phosphinidene functionality. Structural, spectroscopic, theoretical, and catalytic studies addressing the Ti-P multiple bond

Alpha-hydrogen abstraction and alpha-hydrogen migration reactions yield novel titanium(IV) complexes bearing terminal phosphinidene ligands. Via an alpha-H migration reaction, the phosphinidene ((tBu)nacnac)Ti=P[Trip](CH(2)(tBu) ((tBu)nacnac(-) = [Ar]NC((t)Bu)CHC((t)Bu)N[Ar], Ar = 2,6-(CHMe2)(2C6H3, Trip = 2,4,6-(i)Pr3C6H2) was prepared by the addition of the primary phosphide LiPH[Trip] to the nucleophilic alkylidene triflato complex ((tBu)nacnac)Ti=CH(t)Bu(OTf), while alpha-H abstraction was promoted by the addition of LiPH[Trip] to the dimethyl triflato precursor ((tBu)nacnac)Ti(CH)(2)(OTf) to afford ((tBu)nacnac)Ti=P[Trip](CH3). Treatment of ((tBu)nacnac)Ti=P[Trip](CH3) with B(C6F5)(3) induces methide abstraction concurrent with formation of the first titanium(IV) phosphinidene zwitterion complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5)(3)}. Complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5)(3)} [2 + 2] cycloadds readily PhCCPh to afford the phosphametallacyclobutene [((tBu)nacnac)Ti(P[Trip]PhCCPh)][CH3B(C6F5)(3)]. These titanium(IV) phosphinidene complexes possess the shortest Ti=P bonds reported, have linear phosphinidene groups, and reveal significantly upfielded solution 31P NMR spectroscopic resonances for the phosphinidene phosphorus. Solid state 31P NMR spectroscopic data also corroborate with all three complexes possessing considerably shielded chemical shifts for the linear and terminal phosphinidene functionality. In addition, high-level DFT studies on the phosphinidenes suggest the terminal phosphinidene linkage to be stabilized via a pseudo Ti[triple bond]P bond. Linearity about the Ti-P-C(ipso) linkage is highly dependent on the sterically encumbering substituents protecting the phosphinidene. Complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5))(3)} can catalyze the hydrophosphination of PhCCPh with H(2)PPh to produce the secondary vinylphosphine HP[Ph]PhC=CHPh. In addition, we demonstrate that this zwitterion is a powerful phospha-Staudinger reagent and can therefore act as a carboamination precatalyst of diphenylacetylene with aldimines.     

Metallacycles of iron, zinc, and cadmium assembled by polytopic bis(pyrazolyl)methane ligands and fluoride abstraction from BF4-

Reactions of the arene-linked bis(pyrazolyl)methane ligands m-bis[bis(1-pyrazolyl)methyl]benzene (m-[CH(pz)2]2C6H4, Lm) and 1,3,5-tris[bis(1-pyrazolyl)methyl]benzene (1,3,5-[CH(pz)2]3C6H3, L3) with BF4- salts of divalent iron, zinc, and cadmium result in fluoride abstraction from BF4- and formation of fluoride-bridged metallacyclic complexes. Treatment of Fe(BF4)2.6H2O and Zn(BF4)2.5H2O with Lm leads to the complexes [Fe2(mu-F)(mu-Lm)2](BF4)3 (1) and [Zn2(mu-F)(mu-Lm)2](BF4)3 (2), in which a single fluoride ligand and two Lm molecules bridge the two metal centers. The reaction of [Cd2(thf)5](BF4)4 with Lm results in the complex [Cd2(mu-F)2(mu-Lm)2](BF4)2 (3), which contains dimeric cations in which two fluoride and two Lm ligands bridge the cadmium centers. Equimolar amounts of the tritopic ligand L3 and Zn(BF4)2.5H2O react to give the related monofluoride-bridged complex [Zn2(mu-F)(mu-L3)2](BF4)3 (4), in which one bis(pyrazolyl)methane unit on each ligand remains unbound. NMR spectroscopic studies show that in acetonitrile the zinc metallacycles observed in the solid-state remain intact in solution.     

Modeling Tyrosinase Monooxygenase Activity. Spectroscopic and Magnetic Investigations of Products Due to Reactions between Copper(I) Complexes of Xylyl-Based Dinucleating Ligands and Dioxygen: Aromatic Ring Hydroxylation and Irreversible Oxidation Products

A full account of a chemical system possessing features that mimic the reactivity aspects of tyrosinase is presented. Using dinucleating ligands with a m-xylyl spacer three new dicopper(I) complexes have been synthesized and their reactivity with dioxygen investigated. The six-membered chelate ring forming ligands provide only two nitrogen coordinations to each copper. The complexes [Cu(I)(2)L(CH(3)CN)(2)]X(2) (X = ClO(4)(-) (1a), SbF(6)(-) (1b)) and [Cu(I)(2)(L-NO(2))(CH(3)CN)(2)][SbF(6)](2) (1c) [L = alpha,alpha'-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylene; L-NO(2) = para-nitro derivative of L] have been characterized by IR and (1)H NMR spectroscopy. The reaction of O(2) with 1a-c in CH(2)Cl(2) or THF is instantaneous and causes stoichiometric xylyl hydroxylation reactions producing phenol products. Thus 1a produces phenoxo-/hydroxo-bridged product [Cu(II)(2)(L-O)(OH)][ClO(4)](2) (2a). The existence of putative peroxo-dicopper(II) species could not be detected even at -80 degrees C. A trend is observed for the extent of aromatic ring hydroxylation (298 K): CH(3)CN approximately DMF > CH(3)OH > CH(2)Cl(2). Cyclic voltammetric experiment of 1a in DMF reveals an appreciably low redox potential (E(1/2) = -0.26 V vs SCE) for the Cu(II)(2)/Cu(I)(2) redox process. Variable-temperature (25-300 K) magnetic susceptibility measurements establish that the copper(II) centers in 2a and the dihydroxo-bridged complex [Cu(II)(2)L'(OH)(2)][ClO(4)](2) (2b) [formed due to an impurity (L') present during the synthesis of L following Method A; L' = bis[alpha,alpha'-bis(N-methyl-N-(2-pyridylethyl)amino)-m-xylene]methylamine] are antiferromagnetically coupled, with 2a considerably more coupled than 2b. Reaction of 1a with O(2) in CH(2)Cl(2) (298 K) produces an additional unhydroxylated product of composition [Cu(II)(2)L(OH)(OH(2))][ClO(4)](3).2H(2)O.0.5HCl (3a). In agreement with its proposed hydroxo-/aquo-bridged structure, 3a is weakly antiferromagnetically coupled. In CH(3)CN solution, 3a rearranges to generate a doubly hydroxo-bridged species [Cu(II)(2)L(OH)(2)](2+). Using a solution-generated dicopper(I) complex of a closely similar ligand (L' ') providing five-membered chelate ring, the reactivity toward dioxygen was also investigated. It produces only an irreversibly oxidized product of composition Cu(II)(2)L' '(OH)(ClO(4))(3)(H(2)O)(2) (3b) (L' ' = alpha,alpha'-bis[N-methyl-N-(2-pyridylmethyl)amino]-m-xylene). For 3b the copper(II) centers are almost uncoupled.     

Synthesis of neutral (Pd(II), Pt(II)), cationic (Pd(II)), and water-induced anionic (Pd(II)) complexes containing new mesocyclic thioether-aminophosphonite ligands and their application in the Suzuki cross-coupling reaction

Mesocyclic thioether-aminophosphonite ligands, {-OC10H6(mu-S)C10H6O-}PNC4H8O (2a, 4-(dinaphtho[2,1-d:1',2'-g][1,3,6,2]dioxathiaphosphocin-4-yl)morpholine) and {-OC10H6(mu-S)C10H6O-}PNC4H8NCH3 (2b, 1-(dinaphtho[2,1-d:1',2'-g][1,3,6,2]dioxathiaphosphocin-4-yl)-4-methylpiperazine) are obtained by reacting {-OC10H6(mu-S)C10H6O-}PCl (1) with corresponding nucleophiles. The ligands 2a and 2b react with (PhCN)2PdCl2 or M(COD)Cl2 (M = Pd(II) or Pt(II)) to afford P-coordinated cis-complexes, [{(-OC10H6(mu-S)C10H6O-)PNC4H8X-kappaP}2MCl2] (3a, M = Pd(II), X = O; 3b, M = Pd(II), X = NMe; 4a, M = Pt(II), X = O; 4b, M = Pt(II), X = NMe). Compounds 2a and 2b, upon treatment with [Pd(eta3-C3H5)Cl]2 in the presence of AgOTf, produce the P,S-chelated cationic complexes, [{(-OC10H6(mu-S)C10H6O-)PNC4H8X-kappaP,kappaS}Pd(eta3-C3H5)](CF3SO3) (5a, X = O and 5b, X = NMe). Treatment of 2a and 2b with (PhCN)2PdCl2 in the presence of trace amount of H2O affords P,S-chelated anionic complexes, [{(-OC10H6(mu-S)C10H6O-)P(O)-kappaP,kappaS}PdCl2](H2NC4H8X) (6a, X = O and 6b, X = NMe), via P-N bond cleavage. The crystal structures of compounds 1, 2a, 2b, 4a, and 6a are reported. Compound 6a is a rare example of crystallographically characterized anionic transition metal complex containing a thioether-phosphonate ligand. Most of these palladium complexes proved to be very active catalysts for the Suzuki-Miyaura reaction with excellent turnover number ((TON), up to 9.2 x 10(4) using complex 6a as a catalyst).     

Steric control over the formation of cis and trans bis-chelated palladium(II) complexes using a new series of flexible N,P pyridyl-phosphine ligands

The deprotection of phosphonium chloride salts [PR2(CH2OH)2]+Cl- and subsequent condensation reaction with N-methyl-2-aminopyridine has been carried out to give a series of ligands of the form PR2CH2N(CH3)C5H4N (R=Ph , Cy , t-Bu ) which have been fully characterised either as the pure ligand () or the air stable borane adducts (R=Cy , t-Bu ). The 1:1 reactions of , and with PdCl2(COD) gave the N,P chelate complexes [Pd{PR2CH2N(CH3)C5H4N}Cl2]; the Cy () and t-Bu () complexes were characterised by X-ray crystallography. The bisligated species [Pd{PCy2CH2N(CH3)C5H4N}2Cl2] () was obtained when the reaction was carried out at higher temperatures and the ligands were found to be coordinated to the metal in a trans configuration through the phosphorus donors. Abstraction of the chlorides from the bis-ligated species , using silver salts, resulted in the coordination of the pyridine ring forming the bis-chelate complex [Pd{PCy2CH2N(CH3)C5H4N}2]2+. In comparison, the palladium bis-chelate complex of ligand [Pd{PPh2CH2N(CH3)C5H4N}2]2+ () was shown to form in a cis configuration and was fully characterised by X-ray crystallography.     

Synthesis and structure of tetranuclear orthometallated Pd(II) complexes derived from bis-iminophosphoranes

The reaction of Pd(OAc)2 with bis-iminophosphoranes Ph3P=NCH2CH2CH2N=PPh3 (1a), [C6H4(C(O)N=PPh3)2-1,3] (1b) and [C6H4(C(O)N=PPh3)2-1,2] (1c), gives the orthopalladated tetranuclear complexes [{Pd(mu-Cl){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2]2 (2a) [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3']2 (2b) and [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2']2 (2c). The reaction takes place in CH2Cl2 for 1a, but must be performed in glacial acetic acid for 1b and 1c. The process implies in all cases the activation of a C-H bond on a Ph ring of the phosphonium group, with concomitant formation of endo complexes. This is the expected behaviour for 1a, but for 1b and 1c reverses the exo orientation observed in other ketostabilized iminophosphoranes. The influence of the solvent in the orientation of the reaction is discussed. The dinuclear acetylacetonate complexes [{Pd(acac-O,O'){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2] (3a), [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3'] (3b) and [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2'] (3c) have been obtained from the halide-bridging tetranuclear derivatives. The X-ray crystal structure of [3c.4CHCl3] is also reported.