RESUMO
Transition-metal complexes of cyclopropenes occur as fleeting intermediates of numerous metal-catalyzed organic transformations. A heavier analogue has now been obtained from the reaction of an NHC-stabilized silagermenylidene, bis(1,5-cyclooctadiene)nickel(0), and 1 equiv of N-heterocyclic carbene (NHC). The residual chloro functionality at the germanium end of the coordinated GeâSi moiety of the thus formed 1H-disilagermirene is easily exchanged by treatment with anionic nucleophiles, which provides access to a series of differently substituted Si2Ge-cyclopropenes as nickel complexes in excellent yields. NMR spectroscopic data, X-ray crystallographic analysis, and DFT calculations indicate a coordination mode different from the metallacyclopropane and π-complex extremes of the Dewar-Chatt-Duncanson model: the σ-component of the GeâSi double bond acts as donor and acceptor, leaving behind a nearly unsupported Si-Ge π-bond.
RESUMO
Transition metal π-allyl complexes are key reagents/intermediates of various catalytic and stoichiometric allylation reactions. We now report the first transition metal complex of a heavier allylic π-system. The η3-Si2Ge allyl nickel complex is formally obtained by the oxidative addition of the Si-Cl bond of the heavier vinylidene [R2(Cl)Si-(R)Siâ(NHC)Ge:] to [Ni(COD)2] (R = 2,4,6-triisopropylphenyl; NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; COD = 1,5-cyclooctadiene). Due to geometric constraints, the coordination to the Ni(II) center occurs through the formal SiâGe double bond instead of the residual lone pair of electrons at germanium. In contrast, the Si-N bond of the analogous vinylidene [R2(Me2N)Si-(R)Siâ(NHC)Ge:] (obtained by nucleophilic substitution of Cl by NMe2) does not oxidatively add to Ni(0), and a hydridosilagermene-η2-nickel complex is obtained instead. The formation of this complex necessarily implies the isomerization of the heavier vinylidene to the corresponding heteroalkyne with the Si≡Ge triple bond in the coordination sphere of nickel followed by the activation of a C-H bond of one of the isopropyl groups of an N-heterocyclic carbene (NHC) ligand.
RESUMO
The versatile reactivities of disilenides and digermenide, heavier analogues of vinyl anions, have significantly expanded the pool of silicon and germanium compounds with various unexpected structural motifs in the past two decades. We now report the synthesis and isolation of a cyclic heteronuclear vinyl anion analogue with a Si=Ge bond, potassium silagermenide as stable thf-solvate and 18-c-6 solvate by the KC8 reduction of germylene or digermene precursors. Its suitability as synthon for the synthesis of functional silagermenes is proven by the reactions with chlorosilane and chlorophospane to yield the corresponding silyl- and phosphanyl-silagermenes. X-ray crystallographic analysis, UV/Vis spectroscopy and DFT calculations revealed a significant degree of π-conjugation between N=C and Si=Ge double bonds in the title compound.
RESUMO
Tetrylones (ylidones) represent a class of zero-valent groupâ 14 compounds with the general formula EL2 (E=C, Si, Ge, Sn, or Pb; L=neutral σ-donating ligand), wherein the tetrel atom, E(0), possess its four valence electrons in the form of two electron lone pairs, and is moreover coordinated by two ligands (L) via donor-acceptor interactions (LâEâL). This review focuses on the synthesis, structure, reactivity, and computational examination of the isolable heavier tetrylones (Si, Ge, Sn) that have been discovered recently. A comprehensive review on carbone chemistry is beyond the scope of this review. It should also be noted that tetrylones contain two different types of lone pairs, that is, one that exhibits p-type and one that exhibits s-type characteristics. Different behavior should thus be expected when these lone pairs react with Lewis acids.
RESUMO
Synthesis of 1,1'-bifunctional aminophosphane complexes 3 a-e was achieved by the reaction of Li/Cl phosphinidenoid complex 2 with various primary amines (R=Me, iPr, tBu, Cy, Ph). Deprotonation of complex 3 a (R=Me) with potassium hexamethyldisilazide yielded a mixture of K/NHMe phosphinidenoid complex 4 a and potassium phosphanylamido complex 4 a'. Treatment of complex 3 c (R=tBu) and e (R=Ph) with KHMDS afforded the first examples of K/NHR phosphinidenoid complexes 4 c and e. The reaction of complex 3 c with 2 molar equivalents of KHMDS followed by PhPCl2 afforded complexes 5 c,c', which possess a P2 N-ring ligand. All complexes were characterized by NMR, IR, MS, and microanalysis, and additionally, complexes 3 b-e and 5 c' were scrutinized by single-crystal X-ray crystallography.
RESUMO
Phosphasilenes, P=Si doubly bonded compounds, have received considerable attention due to their unique physical and chemical properties. We report on the synthesis and structure of a chlorophosphasilene coordinated by an N-heterocyclic carbene (NHC), which has the potential of functionalization at the Si-Cl moiety. Treatment of a silylphosphine, ArPH-SiCl2RSi (Ar = bulky aryl group, RSi = Si(SiMe3)3) with two equivalents of Im-Me4 (1,3,4,5-tetramethylimidazol-2-ylidene) afforded the corresponding NHC-coordinated phosphasilene, ArP=SiClRSi(Im-Me4) as a stable compound. Bonding properties of the P=Si bond coordinated to an NHC will be discussed on the basis of theoretical calculations.
Assuntos
Compostos Heterocíclicos com 1 Anel , Metano/análogos & derivados , Silene/química , Compostos Heterocíclicos com 1 Anel/síntese química , Compostos Heterocíclicos com 1 Anel/química , Metano/síntese química , Metano/químicaRESUMO
1-Alkyl-3-methyl-4-diphenylphosphoryl-imidazolium hydrogensulfate (4a,b) (a: R(1) = R(2) = Me; b: R(1) = (i)Pr, R(2) = Me) and 1-alkyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazolium hydrogensulfate (6a,c) (c: R(1) = (n)Bu, R(2) = Me) were obtained selectively and in good yields by oxidative desulfurization of 1-alkyl-3-methyl-4-diphenylphosphino-imidazole-2-thiones (2a,b) and 1-n-butyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazole-2-thione (3c) or 1,3-dimethyl-4-diphenylthiophosphoryl-5-diphenylphosphino-imidazole-2-thione (5a), respectively, with hydrogen peroxide. Synthesis of phosphoryl functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (7a-9a) and (10b-12b) and bis(phosphoryl) functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (13c-15c) and (16a) with low steric demand (methyl, isopropyl, n-butyl) at both N-centers was achieved through deprotonation of imidazolium salts (4a,b) and (6a,c), respectively,-having HSO(4)(-) as a counterion-with potassium tert-butoxide followed by rapid addition of metal pentacarbonyl acetonitrile complexes [M(CO)(5)(CH(3)CN)] (M = Cr, Mo, W). The products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods, and in addition, by single-crystal X-ray structure studies in the cases of 4b, 8a, 15c, and 16a; the latter two reveal imidazole ring bond distance alternation in contrast to 8a.
RESUMO
Metalation reactions were studied of a sterically demanding imidazole derivative, namely, 1-tert-butylimidazole (1), with different metalation reagents and subsequent reaction with diphenylchlorophosphane. The reaction product, 1-tert-butyl-2-diphenylphosphino-imidazole (2), was subjected to oxidation and complexation reactions to yield the corresponding products Ph(2)(Imi)P-E (E = O (3), S (4), Se (5), W(CO)(5) (8)) and in the case of borane-THF the N-BH(3) coordination product 10 was obtained. The analytical data of the new compounds are discussed, including X-ray diffraction studies of 3-5.
RESUMO
The reaction of MesP=CPh2 with the least sterically demanding N-heterocyclic carbene (NHC = IMe) results in formation of the 'abnormal' (C(4)-substituted) 4-phosphino-NHC (1). In contrast, reaction with Me2IMe gives the unprecedented 'normal' C(2) adduct, Me2IMe â P(Mes)=CPh2 (2). Particularly striking is the asymmetric and weak bonding of the NHC to the P=C moiety in 2. DFT calculations indicate that the P=C natural bond order in 2 (1.54) still reflects significant π-character to the bond (cf. MesP=CPh2: NBO = 1.98). Further computational analysis suggests that π-delocalization into the remote C-phenyl substituents is key to stabilizing the NHC adduct.
RESUMO
The study of DNA/BSA interaction and the catalytic potential of four mononuclear oxidoalkoxido vanadium(v) [VVO(L1-4)OEt] (1-4) and one dinuclear oxidoalkoxido mixed-ligand vanadium(v) [{VO(L2)OEt}2(Q)]{Q = 4,4'-bipyridine}(5) complexes, with tridentate binegative aroylazine ligands are reported [where H2L1 = anthranylhydrazone of 2-hydroxy-1-napthaldehyde, H2L2 = salicylhydrazone of 2-hydroxy-1-napthaldehyde, H2L3 = benzoylhydrazone of 2-hydroxy-1-acetonaphthone, H2L4 = anthranylhydrazone of 2-hydroxy-1-acetonaphthone]. All the complexes are characterized by elemental analysis as well as various spectroscopic techniques. Single crystal X-ray diffraction crystallography of 2 reveals that the metal centre is in distorted square pyramidal geometry with O4N coordination spheres, whereas 5 exhibits a distorted octahedral geometry around the metal center. In addition, all the complexes (1-5) show moderate DNA binding propensity which is investigated using UV-vis absorption titration, circular dichroism, thermal denaturation and fluorescence spectral studies. The experimental results show that the complexes effectively interact with CT-DNA through both minor and major groove binding modes, with binding constants ranging from 104-105 M-1. Among 1-5, complexes 3 and 4 show higher binding affinity towards CT-DNA than others and at the same time also exhibit negative ΔTm values of about â¼1.5 and 1.0 °C which resembles the properties shown by cisplatin. All complexes show moderate photo-induced cleavage of pUC19 supercoiled plasmid DNA with complex 3 showing the highest photo induced DNA cleavage activity of â¼48%. In coherence with the DNA interaction studies, 3 and 4 also exhibit good binding affinity towards BSA in the range of 1010-1011 M-1, which is also supported by their ability to quench the tryptophan fluorescence emission spectra of BSA. All the complexes show remarkable photo-induced BSA cleavage activity (>90%) at a complex concentration of 50 µM. The catalytic potential of 1-5 is also tested for the oxidative bromination of styrene, salicylaldehyde and oxidation of methyl phenyl sulphide. All the reactions show a high percentage of conversion (>90%) with a high turnover frequency (TOF). Particularly, in the oxidative bromination of styrene the percentage of conversion and TOF vary from 96-98% and 8000-19 600 (h-1) respectively, which signifies the potential of these oxidovanadium(v) complexes to stimulate research for the synthesis of a better catalyst.
Assuntos
Clivagem do DNA , DNA/química , Compostos Organometálicos/química , Soroalbumina Bovina/química , Vanádio/química , Aldeídos/química , Catálise , Dicroísmo Circular , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Naftalenos/química , Compostos Organometálicos/síntese química , Processos Fotoquímicos , Ligação Proteica , Piridinas/química , Estireno/químicaRESUMO
Synthesis of the first P(V)-bridged bis(NHC) ligand 7 was achieved via deprotonation of P(V)-functionalized bis(imidazolium) salt 6, which was obtained via oxidative desulfurization of bis(imidazole-2-thion-4-yl)phosphane 2. Bis(imidazolium) salt 6 was also employed to synthesize the corresponding silver complex 8. All new products were firmly established by spectroscopic and spectrometric methods as well as elemental analysis and, in addition, X-ray crystal structure analysis in the case of 3.
RESUMO
A synthetic route to C(4/5)-bis(phosphinoyl)imidazole-2-thiones (7d,e) (d: R(1) = (n)Bu, R(2) = Me; e: R(1) = n-dodecyl, R(2) = Me) and C(4/5)-bis(thio/selenophosphinoyl)imidazole-2-thiones (8b,c), (9a,b,e) and 10a (a: R(1) = R(2) = Me; b: R(1) = R(2) = Ph, c: R(1) = (i)Pr, R(2) = Me) is presented that employs initial C(5) lithiation of mono-phosphinoyl/thiophosphinoyl substituted imidazole-2-thiones (3c-e)/(4a-c,e) followed by reaction with chlorodiphenylphosphane, leading to mixed phosphinoyl and phosphanyl substituted imidazole-2-thiones (5c-e) or mixed thiophosphinoyl and phosphanyl substituted imidazole-2-thiones (6a-c,e). Subsequent oxidation of mixed phosphinoyl and phosphanyl substituted imidazole-2-thione (5d,e) with H2O2-urea gives the bis(phosphinoyl) substituted imidazole-2-thiones (7d,e), and the oxidation of mixed thiophosphinoyl and phosphanyl substituted imidazole-2-thione (6a-c,e) using H2O2-urea, elemental sulfur or elemental selenium gives a set of mixed P(V)-chalcogenide substituted imidazole-2-thiones (8b,c), (9a,b,e) and 10a, respectively. P(V,V) substituted imidazole-2-thiones 7d and 9a reacted with tellurium tetrachloride, titanium tetrachloride or palladium dichloride to give complexes 11d, (12d and 12d') and 14a, respectively, having a bidentate chelate (11d and 14a) or a monodentate bonding motif (12d,d'). The titanium complexes 12d,d' slowly and selectively converted into the mono-ethoxy substituted product 13 possessing a seven membered chelate motif being unprecedented in the titanium chemistry of phosphine oxide donor ligands. The compounds were characterized by elemental analyses, spectroscopic and spectrometric methods and, in addition, X-ray diffraction studies in the case of 5c, 7d, 8b, 9a and 13.
RESUMO
Selective formation of 4-phosphanylated 1,2-dialkyl imidazole-2-thiones 3a-f has been obtained via a lithiation followed by phosphanylation reaction. The reactivity of 3a-f was examined towards oxidation and complexation reactions. All products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods including X-ray analysis (3a, 3b, 4b, 4d, 5b, 6a and 6d).