Acidites et complexes des acides (alkyl-et aminoalkyl-) phosphoniques-IV: acides aminoalkylphosphoniques R(1)R(2)N(CH(2))(n)CR(3)R(4)PO(3)H(2)

The acids under study differed from one another in length of the carbon chain [N + H(3)(CH(2))(n)PO(3)H(-) for n = 1, 2, 3], substitution on the nitrogen atom [R(1)R(2)N + HCH(2)PO(3)H(-) for R(1) = H; R(2) = Me, Et and R(1) = R(2)= Me, Et] or extent of branching on the carbon atom adjacent to functional groups [N + H(3)CR(3)R(4)PO(3)H(-) for R(3) = H; R(4) = Me, Et, nPr, iPr, nBu and R(3) = R(4) = Me]. Acidity constants and overall stability constants of complexes formed with Ca(II), Mg(II), Co(II), Ni(II), Cu(II), Zn(II) were obtained with the multiparametric refinement programs MUPROT and MUCOMP, applied to potentiometric data, obtained at 25 degrees , in a 0.1M potassium nitrate medium. In the most general case, the existing species are MHA(+), MA, M(OH)A(-), MH(2)A(2), MHA(-)(2) and MA(2-)(2), where A(2-) stands for the fully ionized ligand; preliminary examination of results points out some predominant microscopic forms.     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.     

Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound

The reactivity of several transition metal half sandwich complexes towards an anionic gallium(I) heterocyclic complex, [K(tmeda)][Ga{[N(Ar)C(H)]2}](Ar = C6H3Pri2-2,6), has been investigated. This has led to the anionic half sandwich complexes, [K(tmeda)][(C5H4R)M(CO)n[Ga{[N(Ar)C(H)]2}]](M = V, R = H, n= 3; M = Mn, R = Me, n= 2; M = Co, R = H, n= 1), which crystallographic studies show to form dimers (M = Mn and Co) or a polymer (M = V) through bridging potassium cations. The metal-gallium bond lengths in all complexes are very short which, combined with some spectroscopic evidence, is suggestive of M-Ga pi-bonding. Density functional theory studies of models of all complexes indicate that the level of back-bonding in these complexes is, however, minimal and of a similar order to that seen in analogous complexes incorporating neutral N-heterocyclic carbene ligands. Reactions of the metallocenes, [M(C5H4Me)2](M = V or Cr), with the digallane4, [Ga{[N(Ar)C(H)]2}]2, have afforded the neutral complexes, [M(C5H4Me)2[Ga{[N(Ar)C(H)]2}]], which are thought to be formed via an initial oxidative insertion of the transition metal centre into the Ga-Ga bond of the digallane. X-Ray crystallography shows the complexes to be monomeric. One (M = V) reacts with one equivalent of [K(tmeda)][Ga{[N(Ar)C(H)]2}] to give the crystallographically characterised, anionic bis(gallyl)-complex, [K(tmeda)][V(C5H4Me)2[Ga{[N(Ar)C(H)]2}]2]. For comparison, the reaction of [K(tmeda)][Ga{[N(Ar)C(H)]2}] with [Mn{CH(SiMe3)2}2] was carried out and gave the monomeric, anionic complex, [K(tmeda)][Mn{CH(SiMe3)2}2[Ga{[N(Ar)C(H)]2}]].     

Bimetallic fluorine-substituted anilido-aldimine zinc complexes for CO2/(cyclohexene oxide) copolymerization

Regioselective nucleophilic aromatic substitution of an o-fluorine occurs to afford fluorine-substituted o-phenylene-bridged bis(anilido-aldimine) compounds o-C6H4[(C6H2R2)N=CH-C6F4-(H)N(C6H3R'2)]2 when Li(H)N-C6H3R'2 (R' = iPr, Et, Me) is reacted with o-C6H4[(C6H2R2)N=CH-C6F5]2 (R = iPr, Et, Me) in a nonpolar solvent such as diethyl ether or toluene. Successive additions of Me2Zn and SO2 gas to the bis(anilido-aldimine) compounds afford quantitatively dinuclear mu-methylsulfinato zinc complexes o-C6H4[[(C6H2R2)N=CH-C6F4-N(C6H3R'2)-kappa2N,N]Zn(mu-OS(O)Me)]2 (R = iPr, R' = iPr, 3a; R = iPr, R' = Me, 3c; R = Et, R' = (i)Pr, 3d; R = Et, R' = Et, 3e; R = Et, R' = Me, 3f; R = Me, R' = iPr, 3g; R = Me, R' = Et, 3h; R = Me, R' = Me, 3i). The molecular structure of 3c was confirmed by X-ray crystallography. Fluorine-substituted complexes 3a-i show significantly higher TOF (turnover frequencies) than the unfluorinated analogues for CO2/(cyclohexene oxide) copolymerization. The TOF is highly sensitive to the substituents R and R', and the highest TOF (2480 h(-1)) is obtained with 3g (R = Me, R' = iPr). Complex 3g is less sensitive to the residual protic impurities present in the monomers and shows activity at such a low catalyst concentration as [Zn]:[cyclohexene oxide] = 1:50,000, at which the unfluorinated analogue is completely inactive. By realizing the activity at such an extremely low [Zn]:[cyclohexene oxide] ratio, we achieve a high TON (turnover number) up to 10,100. High-molecular-weight polymers (M(n), 100,000-200,000) are obtained with a rather broad molecular-weight distribution (M(w)/M(n), 1.3-2.5). The obtained polymers are not perfectly alternating, and variable carbonate linkages (65-85%) are observed depending on the N-aryl ortho substituents R and R' and the polymerization conditions.     

Reactivity of 2-pyridinecarboxylic esters with cadmium(II) halides: study of (113)Cd NMR solid state spectra and crystal structures of hexacoordinated complexes [CdI(2)(C(5)H(4)NCOOMe)(2)] and [CdI(2)(C(5)H(4)NCOOPr(n))(2)

The series of complexes [CdX(2)(C(5)H(4)NCOOR)] (X = Cl or Br; R = Me, Et, Pr(n)() or Pr(i)()) and [CdX(2)(C(5)H(4)NCOOR)(2)] (X = I; R = Me, Et, Pr(n)(), or Pr(i)()) have been obtained by the addition reaction of esters of 2-pyridinecarboxylic acid to cadmium(II) halides. X-ray crystal structures of two complexes [CdI(2)(C(5)H(4)NCOOR)(2)], R = Me (10) and R = Pr(n)() (12), have been determined. In both cases, the structure consists of discrete neutral monomeric units where the cadmium atom has a distorted octahedral coordination with CdI(2)N(2)O(2) core, two halides being in cis disposition. Structural information is compared with that deduced from (113)Cd CPMAS NMR experiments. Chemical shift anisotropies are discussed in terms of distortions produced in cadmium octahedra. The orientation of the principal axes of (113)Cd shielding tensor is also analyzed and related to the disposition of ligands in the structures of two analyzed compounds.     

Synthesis and characterisation of mixed ligand Pt(II) and Pt(IV) oxadiazoline complexes

The nitrile ligands in trans-[PtX2(PhCN)2] (X = Cl, Br, I) undergo sequential 1,3 dipolar cycloadditions with nitrones R1R2C=N+(Me)-O(-) (R1 = H, R2 = Ph; R1 = CO2Et, R2 = CH2CO2Et) to selectively form the Delta4-1,2,4-oxadiazoline complexes trans-[PtX2(PhCN) (N=C(Ph)-O-N(Me)-CR1R2)] or trans-[PtX2(N=C(Ph)-O-N(Me)-CR1R2)2] in high yields. The reactivity of the mixed ligand complexes trans-[PtX2(PhCN)(N=C(Ph)-O-N(Me)-CR1R2)] towards oxidation and ligand substitution was studied in more detail. Oxidation with Cl2 or Br2 provides the Pt(IV) species trans-[PtX2Y2(PhCN)(N=C(Ph)-O-N(Me)-CH(Ph))] (X, Y = Cl, Br). The mixed halide complex (X = Cl, Y = Br) undergoes halide scrambling in solution to form trans-[PtX(4-n)Yn(PhCN)(N=C(Ph)-O-N(Me)-CH(Ph))] as a statistical mixture. Ligand substitution in trans-[PtCl2(PhCN)(N=C(Ph)-O-N(Me)-CR1R2)] allows for selective replacement of the coordinated nitrile by nitrogen heterocycles such as pyridine, DMAP or 1-benzyl-2-methylimidazole to produce mixed ligand Pt(II) complexes of the type trans- [PtX2(heterocycle)(N=C(Ph)-O-N(Me)-CR1R2)]. All compounds were characterised by elemental analysis, mass spectrometry, IR and 1H, 13C and 195Pt NMR spectroscopy. Single-crystal X-ray structural analysis of (R,S)-trans-[PtBr2(N=C(Ph)-O-N(Me)-CH(Ph))2] and trans-[PtCl2(C5H5N)(N=C(Ph)-O-N(Me)-CH(Ph))] confirms the molecular structure and the trans configuration of the heterocycles relative to each other.     

Synthesis and reactivity of calix[4]arene-supported group 4 imido complexes

New mononuclear titanium and zirconium imido complexes [M(NR)(R'(2)calix)] [M=Ti, R'=Me, R=tBu (1), R=2,6-C(6)H(3)Me(2) (2), R=2,6-C(6)H(3)iPr(2) (3), R=2,4,6-C(6)H(2)Me(3) (4); M=Ti, R'=Bz, R=tBu (5), R=2,6-C(6)H(3)Me(2) (6), R=2,6-C(6)H(3)iPr(2) (7); M=Zr, R'=Me, R=2,6-C(6)H(3)iPr(2) (8)] supported by 1,3-diorganyl ether p-tert-butylcalix[4]arenes (R'(2)calix) were prepared in good yield from the readily available complexes [MCl(2)(Me(2)calix)], [Ti(NR)Cl(2)(py)(3)], and [Ti(NR)Cl(2)(NHMe(2))(2)]. The crystallographically characterised complex [Ti(NtBu)(Me(2)calix)] (1) reacts readily with CO(2), CS(2), and p-tolyl-isocyanate to give the isolated complexes [Ti[N(tBu)C(O)O](Me(2)calix)] (10), [[Ti(mu-O)(Me(2)calix)](2)] (11), [[Ti(mu-S)(Me(2)calix)](2)] (12), and [Ti[N(tBu)C(O)N(-4-C(6)H(4)Me)](Me(2)calix)] (13). In the case of CO(2) and CS(2), the addition of the heterocumulene to the Ti-N multiple bond is followed by a cycloreversion reaction to give the dinuclear complexes 11 and 12. The X-ray structure of 13.4(C(7)H(8)) clearly establishes the N,N'-coordination mode of the ureate ligand in this compound. Complex 1 undergoes tert-butyl/arylamine exchange reactions to form 2, 3, [Ti(N-4-C(6)H(4)Me)(Me(2)calix)] (14), [Ti(N-4-C(6)H(4)Fc)(Me(2)calix)] (15) [Fc=Fe(eta(5)-C(5)H(5))(eta(5)-C(5)H(4))], and [[Ti(Me(2)calix)](2)[mu-(N-4-C(6)H(4))(2)CH(2)]] (16). Reaction of 1 with H(2)O, H(2)S and HCl afforded the compounds [[Ti(mu-O)(Me(2)calix)](2)] (11), [[Ti(mu-S)(Me(2)calix)](2)] (12), and [TiCl(2)(Me(2)calix)] in excellent yields. Furthermore, treatment of 1 with two equivalents of phenols results in the formation of [Ti(O-4-C(6)H(4)R)(2)(Me(2)calix)] (R=Me 17 or tBu 18), [Ti(O-2,6-C(6)H(3)Me(2))(2)(Me(2)calix)] (19) and [Ti(mbmp)(Me(2)calix)] (20; H(2)mbmp=2,2'-methylene-bis(4-methyl-6-tert-butylphenol) or CH(2)([CH(3)][C(4)H(9)]C(6)H(2)-OH)(2)). The bis(phenolate) compounds 17 and 18 with para-substituted phenolate ligands undergo elimination and/or rearrangement reactions in the nonpolar solvents pentane or hexane. The metal-containing products of the elimination reactions are dinuclear complexes [[Ti(O-4-C(6)H(4)R)(Mecalix)](2)] [R=Me (23) or tBu (24)] where Mecalix=monomethyl ether of p-tert-butylcalix[4]arene. The products of the rearrangement reaction are [Ti(O-4-C(6)H(4)Me)(2) (paco-Me(2)calix)] (25) and [Ti(O-4-C(6)H(4)tBu)(2)(paco-Me(2)calix)] (26), in which the metallated calix[4]arene ligand is coordinated in a form reminiscent of the partial cone (paco) conformation of calix[4]arene. In these compounds, one of the methoxy groups is located inside the cavity of the calix[4]arene ligand. The complexes 24, 25 and 26 have been crystallographically characterised. Complexes with sterically more demanding phenolate ligands, namely 19 and 20 and the analogous zirconium complexes [Zr(O-4-C(6)H(4)Me)(2)(Me(2)calix)] (21) and [Zr(O-2,6-C(6)H(3)Me(2))(2)(Me(2)calix)] (22) do not rearrange. Density functional calculations for the model complexes [M(OC(6)H(5))(2)(Me(2)calix)] with the calixarene possessing either cone or partial cone conformations are briefly presented.     

Bimetallic anilido-aldimine zinc complexes for epoxide/CO2 copolymerization

Acyclic o-phenylene-bridged bis(anilido-aldimine) compounds, o-C(6)H(4){C(6)H(2)R(2)N=CH-C(6)H(4)-(H)N(C(6)H(3)R'(2))}(2) and related 30-membered macrocyclic compounds, o-C(6)H(4){C(6)H(2)R'(2)N=CH-C(6)H(4)-(H)N-C(6)H(2)R(2)}(2) (o-C(6)H(4)) are prepared. Successive additions of Me(2)Zn and SO(2) gas to the bis(anilido-aldimine) compounds afford quantitatively dinuclear mu-methylsulfinato zinc complexes, o-C(6)H(4){(C(6)H(2)R(2)N=CH-C(6)H(4)-N(C(6)H(3)R'(2))-kappa(2)-N,N)Zn(mu-OS(O)Me)}(2) (R = iPr and R' = iPr, 29; R = Et and R' = Et, 30; R = Me and R'= Me, 31; R = Me and R' = iPr, 32; R = Et and R' = Me, 33; R = Et and R' = iPr, 34; R = iPr and R' = Et, 35) and o-C(6)H(4){C(6)H(2)R'(2)N=CH-C(6)H(4)-N-C(6)H(2)R(2)-kappa(2)-N,N)Zn(mu-OS(O)Me)}(2) (o-C(6)H(4)) (R = Et and R'= Et, 36; R = Me and R' = Me, 37; R = iPr and R' = Me, 38; R = Et and R' = Me, 39; R = Me and R'= iPr, 40). Molecular structures of 34 and 40 are confirmed by X-ray crystallography. Complexes 30-35 show high activity for cyclohexene oxide/CO(2) copolymerization at low [Zn]/[monomer] ratio (1:5600), whereas the complex of mononucleating beta-diketiminate {[(C(6)H(3)Et(2))N=C(Me)CH=C(Me)N(C(6)H(3)Et(2))]Zn(mu-OS(O)Et)}(2) shows negligible activity in the same condition. Activity is sensitive to the N-aryl ortho substituents and the highest activity is observed with 32. Turnover number up to 2980 and molecular weight (M(n)) up to 284 000 are attained with 32 at such a highly diluted condition as [Zn]/[monomer] = 1:17 400. Macrocyclic complexes 36-40 show negligible activity for copolymerization.     

Group 13 β-ketoiminate compounds: gallium hydride derivatives as molecular precursors to thin films of Ga2O3

Bis(β-ketoimine) ligands, [R{N(H)C(Me)-CHC(Me)═O}(2)] (L(1)H(2), R = (CH(2))(2); L(2)H(2), R = (CH(2))(3)), linked by ethylene (L(1)) and propylene (L(2)) bridges have been used to form aluminum, gallium, and indium chloride complexes [Al(L(1))Cl] (3), [Ga(L(n))Cl] (4, n = 1; 6, n = 2) and [In(L(n))Cl] (5, n = 1; 7, n = 2). Ligand L(1) has also been used to form a gallium hydride derivative [Ga(L(1))H] (8), but indium analogues could not be made. β-ketoimine ligands, [Me(2)N(CH(2))(3)N(H)C(R')-CHC(R')═O] (L(3)H, R' = Me; L(4)H, R' = Ph), with a donor-functionalized Lewis base have also been synthesized and used to form gallium and indium alkyl complexes, [Ga(L(3))Me(2)] (9) and [In(L(3))Me(2)] (10), which were isolated as oils. The related gallium hydride complexes, [Ga(L(n))H(2)] (11, n = 3; 12, n = 4), were also prepared, but again no indium hydride species could be made. The complexes were characterized mainly by NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction. The β-ketoiminate gallium hydride compounds (8 and 11) have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted (AA)CVD with toluene as the solvent. The quality of the films varied according to the precursor used, with the complex [Ga(L(1))H] (8) giving by far the best quality films. Although the films were amorphous as deposited, they could be annealed at 1000 °C to form crystalline Ga(2)O(3). The films were analyzed by powder XRD, SEM, and EDX.     

Zinc complexes of Ttz(R,Me) with O and S donors reveal differences between Tp and Ttz ligands: acid stability and binding to H or an additional metal (Ttz(R,Me) = tris(3-R-5-methyl-1,2,4-triazolyl)borate; R = Ph, tBu)

Alkylzinc complexes, (Ttz(R,Me))ZnR' (R = tBu, Ph; R' = Me, Et), show interesting reactivity with acids, bases and water. With acids (e.g. fluorinated alcohols, phenols, thiophenol, acetylacetone, acetic acid, HCl and triflic acid) zinc complexes of the conjugate base (CB), (Ttz(R,Me))ZnCB, are generated. Thus the B-N bonds in Ttz ligands are acid stable. (Ttz(R,Me))ZnCB complexes were characterized by (1)H, (13)C-NMR, IR, MS, elemental analysis, and, in most cases, single crystal X-ray diffraction. The four coordinate crystal structures included (Ttz(R,Me))Zn(CB) [where R = Ph, CB (conjugate base) = OCH(2)CF(3) (2), OPh (6), SPh (8), p-OC(6)H(4)(NO(2)) (10); R = tBu, CB = OCH(CF(3))(2) (3), OPh (5), SPh (7)*, p-OC(6)H(4)(NO(2)) (9) (* indicates a rearranged Ttz ligand)]. The use of bidentate ligands resulted in structures [(Ttz(Ph,Me))Zn(CB) (CB = acac (12), OAc (14))] in which the coordination geometries are five, and intermediate between four and five, respectively. Interestingly, three forms of (Ttz(Ph,Me))Zn(p-OC(6)H(4)(NO(2))) (10) were analyzed crystallographically including a Zn coordinated water molecule in 10(H(2)O), a coordination polymer in 10(CP), and a p-nitrophenol molecule hydrogen bonded to a triazole ring in 10(Nit). Ttz ligands are flexible since they are capable of providing κ(3) or κ(2) metal binding and intermolecular interactions with either a metal center or H through the four position nitrogen (e.g. in 10(CP) and HTtz(tBu,Me)·H(2)O, respectively). Preliminary kinetic studies on the protonolysis of LZnEt (L = Ttz(tBu,Me), Tp(tBu,Me)) with p-nitrophenol in toluene at 95 °C show that these reactions are zero order in acid and first order in the LZnEt.     

Reduction of (imine)Pt(IV) to (imine)Pt(II) complexes with carbonyl-stabilized phosphorus ylides

A novel method is reported for generation of the difficult-to-obtain (imine)Pt(II) compounds that involves reduction of the corresponding readily available Pt(IV)-based imines by carbonyl-stabilized phosphorus ylides, Ph3P=CHCO2R, in nonaqueous media. The reaction between neutral (imino)Pt(IV) compounds [PtCl4[NH=C(Me)ON=CR1R2]2] [R1R2 = Me2, (CH2)4, (CH2)5, (Me)C(Me)=NOH], [PtCl4[NH=C(Me)ONR2]2] (R = Me, Et, CH2Ph), (R1 = H; R2 = Ph or C6H4Me; R3 = Me) as well as anionic-type platinum(IV) complexes (Ph3PCH2Ph)[PtCl5[NH=C(Me)ON=CR2]] [R2 = Me2, (CH2)4, (CH2)5] and 1 equiv of Ph3P=CHCO2R (R = Me, Et) proceeds under mild conditions (ca. 4 h, room temperature) to give selectively the platinum(II) products (in good to excellent isolated yields) without further reduction of the platinum center. All thus prepared compounds (excluding previously described Delta4-1,2,4-oxadiazoline complexes) were characterized by elemental analyses, FAB mass spectrometry, IR and 1H, 13C[1H], 31P[1H] and 195Pt NMR spectroscopies, and X-ray single-crystal diffractometry, the latter for [PtCl2[NH=C(Me)ON=CMe2]2] [crystal system tetragonal, space group P4(2)/n (No. 86), a = b = 10.5050(10) A, c = 15.916(3) A] and (Ph3PCH2CO2Me)[PtCl3(NCMe)] [crystal system orthorhombic, space group Pna2(1) (No. 33), a = 19.661(7) A, b = 12.486(4) A, c = 10.149(3) A]. The reaction is also extended to a variety of other Pt(II)/Pt(IV) couples, and the ylides Ph3P=CHCO2R are introduced as mild and selective reducing agents of wide applicability for the conversion of Pt(IV) to Pt(II) species in nonaqueous media, a route that is especially useful in the case of compounds that cannot be prepared directly from Pt(II) precursors, and for the generation of systematic series of Pt(II)/Pt(IV) complexes for biological studies.     

Kinetic and mechanistic study of the Pt(II) versus Pt(IV) effect in the platinum-mediated nitrile-hydroxylamine coupling

The metal-mediated coupling between coordinated EtCN in the platinum(II) and platinum(IV) complexes cis- and trans-[PtCl(2)(EtCN)(2)], trans-[PtCl(4)(EtCN)(2)], a mixture of cis/trans-[PtCl(4)(EtCN)(2)] or [Ph(3)PCH(2)Ph][PtCl(n)(EtCN)] (n = 3, 5), and dialkyl- and dibenzylhydroxylamines R(2)NOH (R = Me, Et, CH(2)Ph, CH(2)C(6)H(4)Cl-p) proceeds smoothly in CH(2)Cl(2) at 20-25 degrees C and the subsequent workup allowed the isolation of new imino species [PtCl(n){NH=C(Et)ONR(2)}(2)] (n = 2, R = Me, cis-1 and trans-1; Et, cis-2 and trans-2; CH(2)Ph, cis-3 and trans-3; CH(2)C(6)H(4)Cl-p, cis-4 and trans-4; n = 4, R = Me, trans-9; Et, trans-10; CH(2)Ph, trans-11; CH(2)C(6)H(4)Cl-p, trans-12) or [Ph(3)PCH(2)Ph][PtCl(n){NH=C(Et)ONR(2)}] (n = 3, R = Me, 5; Et, 6; CH(2)Ph, 7; CH(2)C(6)H(4)Cl-p, 8; n = 5, R = Me, 13; Et, 14; CH(2)Ph, 15; CH(2)C(6)H(4)Cl-p, 16) in excellent to good (95-80%) isolated yields. The reduction of the Pt(IV) complexes 9-16 with the ylide Ph(3)P=CHCO(2)Me allows the synthesis of Pt(II) species 1-8. The compounds 1-16 were characterized by elemental analyses (C, H, N), FAB-MS, IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR (the latter for the anionic type complexes 5-8 and 13-16) and by X-ray crystallography for the Pt(II) (cis-1, cis-2, and trans-4) and Pt(IV) (15) species. Kinetic studies of addition of R(2)NOH (R = CH(2)C(6)H(4)Cl-p) to complexes [Ph(3)PCH(2)Ph][Pt(II)Cl(3)(EtCN)] and [Ph(3)PCH(2)Ph][Pt(IV)Cl(5)(EtCN)] by the (1)H NMR technique revealed that both reactions are first order in (p-ClC(6)H(4)CH(2))(2)NOH and Pt(II) or Pt(IV) complex, the second-order rate constant k(2) being three orders of magnitude larger for the Pt(IV) complex. The reactions are intermolecular in nature as proved by the independence of k(2) on the concentrations of added EtC triple bond N and Cl(-). These data and the calculated values of Delta H++ and Delta S++ are consistent with the mechanism involving the rate-limiting nucleophilic attack of the oxygen of (p-ClC(6)H(4)CH(2))(2)NOH at the sp-carbon of the C triple bond N bond followed by a fast proton migration.     

Distinct reaction pathways of peralkylated LnIIAlIII heterobimetallic complexes with substituted phenols

The protonolysis reaction of heterobimetallic peralkylated complexes [Ln(AlR4)2]n (Ln=Sm, Yb; R=Me, Et) with 2 equiv of HOC 6H 2 tBu 2-2,6-Me-4 affords the bis(trialkylaluminum) adducts Ln[(micro-OArtBu,Me)(micro-R)AlR2]2 in good yields. Analogous reactions with the less sterically demanding iPr-substituted phenol result in ligand redistributions and formation of X-ray structurally evidenced Ln[(micro-OAriPr,H) 2AlR2]2 (Ln=Yb, R=Me; Ln=Sm, R=Et), Yb[(micro-OAriPr,H)(micro-Et)AlEt2]2(THF), and [Et2Al(micro-OAriPr,H) 2Yb(micro-Et)2AlEt2]2. The solid-state structures of serendipitous alumoxane complex Sm[(micro-OArtBu,Me)AlEt2OAlEt2(micro-OArtBu,Me)](toluene) and dimeric AlMe 3-adduct complex [(AlMe3)(micro-OArtBu,Me)Sm(micro-OArtBu,Me) 2Sm(micro-OArtBu,Me)(AlMe3)] were also determined by X-ray crystallography. While the former can be discussed as a typical hydrolysis product of Sm[(micro-OArtBu,Me)(micro-Et)AlEt2]2, the latter was isolated from the 1:1 reaction of [Sm(AlEt4)2]n with HOArtBu,Me.     

Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: efficient synthesis of substituted guanidines through amine protonolysis of rare-earth metal guanidinates

Reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] (Ln=Y, Yb, and Lu) with one equivalent of Me(2)Si(C(5)Me(4)H)NHR' (R'=Ph, 2,4,6-Me(3)C(6)H(2), tBu) affords straightforwardly the corresponding half-sandwich rare-earth metal alkyl complexes [{Me(2)Si(C(5)Me(4))(NR')}Ln(CH(2)SiMe(3))(thf)(n)] (1: Ln = Y, R' = Ph, n=2; 2: Ln = Y, R' = C(6)H(2)Me(3)-2,4,6, n=1; 3: Ln = Y, R' = tBu, n=1; 4: Ln = Yb, R' = Ph, n=2; 5: Ln = Lu, R' = Ph, n=2) in high yields. These complexes, especially the yttrium complexes 1-3, serve as excellent catalyst precursors for the catalytic addition of various primary and secondary amines to carbodiimides, efficiently yielding a series of guanidine derivatives with a wide range of substituents on the nitrogen atoms. Functional groups such as C[triple chemical bond]N, C[triple chemical bond]CH, and aromatic C--X (X: F, Cl, Br, I) bonds can survive the catalytic reaction conditions. A primary amino group can be distinguished from a secondary one by the catalyst system, and therefore, the reaction of 1,2,3,4-tetrahydro-5-aminoisoquinoline with iPrN==C==NiPr can be achieved stepwise first at the primary amino group to selectively give the monoguanidine 38, and then at the cyclic secondary amino unit to give the biguanidine 39. Some key reaction intermediates or true catalyst species, such as the amido complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y(NEt(2))(thf)(2)] (40) and [{Me(2)Si(C(5)Me(4))(NPh)}Y(NHC(6)H(4)Br-4)(thf)(2)] (42), and the guanidinate complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrNC(NEt(2))(NiPr)}(thf)] (41) and [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrN}C(NC(6)H(4)Br-4)(NHiPr)}(thf)] (44) have been isolated and structurally characterized. Reactivity studies on these complexes suggest that the present catalytic formation of a guanidine compound proceeds mechanistically through nucleophilic addition of an amido species, formed by acid-base reaction between a rare-earth metal alkyl bond and an amine N--H bond, to a carbodiimide, followed by amine protonolysis of the resultant guanidinate species.     

Di-μ-hydroxo complexes of palladium(II) with α-diimines

The binuclear hydroxo α-diiminate palladium complexes [Pd2(R′N=CR-CR=NR′)2(μ-OH)2][ClO4]2 (R=H, R′= C6H4Me-o or C6H4Me-p; R=Me, R′=Ph, C6H4Me-o or C6H4Me-p) have been prepared by reacting the corresponding chloro complexes with AgClO4 in Me2CO–H2O. The hydroxo complexes react with the protic electrophiles ethanoic acid, acetylacetone and8-hydroxoquinoline to give the corresponding acetylacetonate, acetate and 8-hydroxiquinolinate complexes. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis and characterization of tetrahedral and square planar Bis(iminopyrrolyl) complexes of cobalt(II)

A series of 2-iminopyrrole ligand precursors with increasing bulkiness [HNC4H3C(R)=N-2,6-R'2C6H3] (R = R' = H, 1a; R = Me, R'= H, 1b; R = H, R' = Me, 1c; R = R' = Me, 1d; R = H, R' = iPr, 1e; R = Me, R' = iPr, 1f) were synthesized and deprotonated with NaH to give the corresponding iminopyrrolyl sodium salts 2a-f. A set of homoleptic bis-ligand Co(II) complexes of the type [Co(kappa2N,N'-NC4H3C(R)=N-2,6-R'2C6H3)2] (R = R'= H, 3a; R = Me, R'= H, 3b; R = H, R' = Me, 3c; R = R' = Me, 3d; R = H, R' = iPr, 3e; R = Me, R' = iPr, 3f) was prepared by reaction of CoCl2 with the corresponding iminopyrrolyl sodium salts 2a-f. The new complexes were characterized by elemental analysis, magnetic susceptibility measurements, in powder and in solution, UV/vis/NIR, and, in some cases, X-ray crystallography. According to X-ray diffraction and magnetic measurements, the Co complexes 3a-e proved to be tetrahedral, which is the preferred geometry for Co(II) compounds. However, a square planar geometry is observed in the case of 3f, as determined by several characterization techniques. In this case, DFT calculations suggest the square planar geometry is slightly more stable than the tetrahedral one probably due to a combination of steric and electronic reasons.     

Synthesis and characterization of pyridine amide cation radical complexes of iron: stabilization due to coordination with low-spin iron(III) center

We reported the synthesis and characterization of peptide complexes of low-spin iron(III) [Fe(bpb)(py)2][ClO4] (1) and Na[Fe(bpb)(CN)2] (2) [H2bpb = 1,2-bis(pyridine-2-carboxamido)benzene; py = pyridine], where iron is coordinated to four nitrogen donors in the equatorial plane with two amide nitrogen anions and two pyridine nitrogen donors (Ray, M.; Mukherjee, R.; Richardson, J. F.; Buchanan, R. M. J. Chem. Soc., Dalton Trans. 1993, 2451). Chemical oxidation of 2 and a new low-spin iron(III) complex Na[Fe(Me6bpb)(CN)2].H2O (4) [synthesized from a new iron(III) complex [Fe(Me6bpb)(py)2][ClO4] (3) (S = 1/2)] [H2Me6bpb = 1,2-bis(3,5-dimethylpyridine2-carboxamido)-4,5-dimethylbenzene) by (NH4)2Ce(NO3)6 afforded isolation of two novel complexes [Fe(bpb)-(CN)2] (5) and [Fe(Me6bpb)(CN)2].H2O (6). All the complexes have been characterized by physicochemical techniques. While 1-4 are brown/green, 5 and 6 are violet/bluish violet. The collective evidence from infrared, electronic, M?ssbauer, and 1H NMR spectroscopies, from temperature-dependent magnetic susceptibility data, and from cyclic voltammetric studies provides unambiguous evidence that 5 and 6 are low-spin iron(III) ligand cation radical complexes rather than iron(IV) complexes. Cyclic voltammetric studies on isolated oxidized complexes 5 and 6 display identical behavior (a metal-centered reduction and a ligand-centered oxidation) to that observed for complexes 2 and 4, respectively. The M?ssbauer data for 6 are almost identical with those of the parent compound 4, providing compelling evidence that oxidation has occurred at the ligand in a site remote from the iron atom. Strong antiferromagnetic coupling (-2J > or = 450 cm(-1)) of the S = 1/2 iron atom with the S = 1/2 ligand pi-cation radical leads to an effectively S = 0 ground state of 5 and 6. The oxidized complexes display 1H NMR spectra (in CDCl3 solution), characteristic of diamagnetic species.     

Self-assembly of dialkyltin moieties and mercaptobenzoic acid into macrocyclic complexes with hydrophobic "pseudo-cage" or double-cavity structures: supramolecular infrastructures involving intermolecular C-H...S weak hydrogen bonds and pi-pi interactions

Four novel organotin complexes of two types--[R2Sn(o-SC6H4CO2)]6 (R = Me, 1 x H2O; nBu, 2) and {[R2Sn(m-CO2C6H4S)R2Sn(m-SC6H4CO2)SnR2]O}2 (R = Me, 3; nBu, 4)--have been prepared by treatment of o- or m-mercaptobenzoic acid and the corresponding R2SnCl2 (R = Me, nBu) with sodium ethoxide in ethanol (95%). All the complexes were characterized by elemental analysis, FT-IR and NMR (1H, (3C, 119Sn) spectroscopy, TGA, and X-ray crystallography diffraction analysis. The molecular structure analyses reveal that both 1 and 2 are hexanuclear macrocycles with hydrophobic "pseudo-cage" structures, while 3 and 4 are hexanuclear macrocycles with double-cavity structures. Furthermore, the supramolecular structure analyses show that looser and more intriguing supramolecular infrastructures were also found in complexes 1-4, which exist either as one-dimensional chains of rings or as two-dimensional networks assembled from the organometallic subunits through intermolecular C-H...S weak hydrogen bonds (WHBs) and pi-pi interactions.     

Stereospecific synthesis of polysubstituted E-olefins by reaction of acyclic nitrones with free and platinum(II) coordinated organonitriles

Free nitriles NCCH2R (1a R = CO2Me, 1b R = SO2Ph, and 1c R = COPh) with an acidic alpha-methylene react with acyclic nitrones -O+N(Me)=C(H)R' (2a R' = 4-MeC6H4 and 2b R' = 2,4,6-Me3C6H2), in refluxing CH2Cl2, to afford stereoselectively the E-olefins (NC)(R)C=C(H)R' (3a-3c and 3a'-3c'), whereas, when coordinated at the platinum(II) trans-[PtCl2(NCCH2R)2] complexes (4a R = CO2Me and 4b R = Cl), they undergo cycloaddition to give the (oxadiazoline)-PtII complexes trans-[PtCl2{N=C(CH2R)ON(Me)C(H)R'}2] (R = CO2Me, Cl and R' = 4-MeC6H4, 2,4,6-Me3C6H2) (5a-5d). Upon heating in CH2Cl2, 5a affords the corresponding alkene 3a. The reactions are greatly accelerated when carried out under focused microwave irradiation, particularly in the solid phase (SiO2), without solvent, a substantial increase of the yields being also observed. The compounds were characterized by IR and 1H, 13C, and 195Pt NMR spectroscopies, FAB+-MS, elemental analyses and, in the cases of the alkene (NC)(CO2Me)C=C(H)(4-MeC6H4) 3a and of the oxadiazoline complex trans-[PtCl2{N=C(CH2Cl)ON(Me)C(H)(4-C6H4Me)}2] 5c, also by X-ray diffraction analyses.     

Hypervalent neutral O-donor ligand complexes of silicon tetrafluoride, comparisons with other group 14 tetrafluorides and a search for soft donor ligand complexes

The hypervalent adducts of SiF(4), trans-[SiF(4)(R(3)PO)(2)] (R = Me, Et or Ph), cis-[SiF(4){R(2)P(O)CH(2)P(O)R(2)}] (R = Me or Ph), cis-[SiF(4)(pyNO)(2)] and trans-[SiF(4)(DMSO)(2)] have been prepared from SiF(4) and the ligands in anhydrous CH(2)Cl(2), and characterised by microanalysis, IR and VT multinuclear ((1)H, (19)F, (31)P) NMR spectroscopy. The NMR studies show extensive dissociation at ambient temperatures in non-coordinating solvents, but mixtures of cis and trans isomers of the monodentate ligand complexes were identified at low temperatures. Crystal structures are reported for trans-[SiF(4)(R(3)PO)(2)] (R = Me or Ph), and cis-[SiF(4)(pyNO)(2)]. The GeF(4) analogues cis-[GeF(4){R(2)P(O)(CH(2))(n)P(O)R(2)}] (R = Me or Ph, n = 1; R = Ph, n = 2) were similarly characterised and the structures of cis-[GeF(4){R(2)P(O)CH(2)P(O)R(2)}] (R = Me or Ph) determined. The reaction of R(3)AsO (R = Me or Ph) with SiF(4) does not give simple adducts, but forms [R(3)AsOH](+) cations as fluorosilicate salts. SiF(4) adducts of some ether ligands (including THF, 12-crown-4) were also characterised by (19)F NMR spectroscopy in solution at low temperatures (～190 K), but are fully dissociated at room temperature. Attempts to isolate, or even to identify, SiF(4) adducts with phosphine or thioether ligands in solution at 190 K were unsuccessful, contrasting with the recent isolation and detailed characterisation of GeF(4) analogues. The chemistry of SiF(4) with these oxygen donor ligands, and with soft donors (P, As, S or Se), is compared and contrasted with those of GeF(4), SnF(4) and SiCl(4). The key energy factors determining stability of these complexes are discussed.