Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand.
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ABSTRACT:
SUBMITTER: Authesserre U
PROVIDER: S-EPMC8037485 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The use of a bis(diphenyl)phosphine functionalized β-diketiminato ligand, [HC{(CH3 )C}2 {(ortho-[P(C6 H5 )2 ]2 C6 H4 )N}2 ]- (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride abstraction from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E]+ in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization. In a similar fashion, chemical decarbonylation of the germanium phosphaketene [(PNac)Ge(PCO)] with tris(pentafluorophenyl)borane affords a "push-pull" stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center.
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Project description:Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)](2)CH). The dinitrosyliron complexes [Fe(NO)(2)(Ar-nacnac)] (1) and (Bu(4)N)[Fe(NO)(2)(Ar-nacnac)] (2) react with [Fe(III)(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [Fe(II)(NO)(TPP)] and the corresponding mononitrosyliron complexes. The factors governing NO transfer with dinitrosyliron complexes (DNICs) 1 and 2 are evaluated, together with the chemistry of the related mononitrosyliron complex, [Fe(NO)Br(Ar-nacnac)] (4). The synthesis and properties of the related cobalt dinitrosyl [Co(NO)(2)(Ar-nacnac)] (3) is also discussed for comparison to DNICs 1 and 2. The solid-state structures of several of these compounds as determined by X-ray crystallography are reported.
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Project description:A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy-N3 N)(arene)] (Xy-N3 N={(3,5-Me2 C6 H3 )NCH2 CH2 }3 N3- , L=THF, 18-crown-6; arene=C10 H8 2- , C14 H10 2- ) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy-N3 N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert-butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2-) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2-) complex led to the selective protonation of the corresponding dianionic ligand.
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Project description:A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac- acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states.
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Project description:Hydrogen bonds (H-bonds) within the secondary coordination sphere are often invoked as essential noncovalent interactions that lead to productive chemistry in metalloproteins. Incorporating these types of effects within synthetic systems has proven a challenge in molecular design that often requires the use of rigid organic scaffolds to support H-bond donors or acceptors. We describe the preparation and characterization of a new hybrid tripodal ligand ([H2pout]3-) that contains two monodeprotonated urea groups and one phosphinic amide. The urea groups serve as H-bond donors, while the phosphinic amide group serves as a single H-bond acceptor. The [H2pout]3- ligand was utilized to stabilize a series of Mn-hydroxido complexes in which the oxidation state of the metal center ranges from 2+ to 4+. The molecular structure of the MnIII-OH complex demonstrates that three intramolecular H-bonds involving the hydroxido ligand are formed. Additional evidence for the formation of intramolecular H-bonds was provided by vibrational spectroscopy in which the energy of the O-H vibration supports its assignment as an H-bond donor. The stepwise oxidation of [MnIIH2pout(OH)]2- to its higher oxidized analogs was further substantiated by electrochemical measurements and results from electronic absorbance and electron paramagnetic resonance spectroscopies. Our findings illustrate the utility of controlling both the primary and secondary coordination spheres to achieve structurally similar Mn-OH complexes with varying oxidation states.
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Project description:Herein, we report the synthesis of a series of heteroleptic magnesium complexes stabilized with the scorpionate ligand tris(2-pyridylthio)methanide (Tptm). The compounds of the general formula [Mg(Tptm)(X)] (1-X; X = Cl, Br, I) were obtained via protonolysis reaction between the proligand and selected Grignard reagents. Attempts to isolate the potassium derivative K(Tptm) lead to decomposition of Tptm and formation of the alkene (C5H4N-S)2C=C(C5H4N-S)2, and this degradation was also modelled using DFT methods. Compound 1-I was treated with K(CH2Ph), affording the degradation product [Mg(Bptm)2] (2; Bptm = {CH(S-C5NH3)2}-). We analyzed and quantified the steric properties of the Tptm ligand using the structural information of the compounds obtained in this study paired with buried volume calculations, also adding the structural data of HTptm and its CF3-substituted congener (HTptmCF3). These studies highlight the highly flexible nature of this ligand scaffold and its ability to stabilize various coordination motifs and geometries, which is a highly desirable feature in the design of novel organometallic reagents and catalysts.
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Project description:The reactions of potassium salts of the dithiocarbamates L {where L = pyrazolyldithiocarbamate (L1), 3,5-dimethylpyrazolyldithiocarbamate (L2), or indazolyldithiocarbamate (L3)} with the gold precursors [AuCl(PPh3)], [Au2Cl2(dppe)], [Au2Cl2(dppp)], or [Au2Cl2(dpph)] lead to the new gold(I) complexes [AuL(PPh3)] (1-3), [Au2L2(dppe)] (4-6), [(Au2L2)(dppp)] (7-9), and [Au2(L)2(dpph)] (10-12) {where dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, and dpph = 1,6-bis(diphenylphosphino)hexane}. These gold compounds were characterized by a combination of NMR and infrared spectroscopy, microanalysis, and mass spectrometry; and in selected cases by single-crystal X-ray crystallography. Compounds 4-6, which have dppe ligands, are unstable in solution for prolonged periods, with 4 readily transforming to the Au18 cluster [Au18S8(dppe)6]Cl2 (4a) in dichloromethane. Compounds 1-3 and 7-12 are all active against human cervical epithelioid carcinoma (HeLa) cells, but the most active compounds are 10 and 11, with IC50 values of 0.51 μM and 0.14 μM, respectively. Compounds 10 and 11 are more selective toward HeLa cells than they are toward normal cells, with selectivities of 25.0 and 70.5, respectively. Further tests, utilizing the 60-cell-line Developmental Therapeutics Program at the National Cancer Institute (U.S.A.), showed 10 and 11 to be active against nine other types of cancers.
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Project description:Three cyclo-penta-dienylmolybdenum(II) propionyl complexes featuring tri-aryl-phosphine ligands with different para substituents, namely, dicarbon-yl(η5-cyclo-penta-dien-yl)propion-yl(tri-phenyl-phosphane-κP)molybdenum(II), [Mo(C5H5)(C3H5O)(C18H15P)(CO)2], (1), dicarbon-yl(η5-cyclo-penta-dien-yl)propion-yl[tris-(4-fluoro-phen-yl)phosphane-κP]molybdenum(II), [Mo(C5H5)(C3H5O)(C18H12F3P)(CO)2], (2), and dicarbon-yl(η5-cyclo-penta-dien-yl)propion-yl[tris-(4-meth-oxy-phen-yl)phosphane-κP]molybdenum(II) dichloromethane solvate, [Mo(C5H5)(C3H5O)(C21H21O3P)(CO)2]·CH2Cl2, (3), have been prepared from the corresponding ethyl complexes via phosphine-induced migratory insertion. These complexes exhibit four-legged piano-stool geom-etries with mol-ecular structures quite similar to each other and to related acetyl complexes. The extended structures of the three complexes differ somewhat, with the para substituent of the tri-aryl-phosphine of (2) (fluoro) or (3) (meth-oxy) engaging in non-classical C-H⋯F or C-H⋯O hydrogen-bonding inter-actions. The structure of (3) exhibits modest disorder in the position of one Cl atom of the di-chloro-methane solvent, which was modeled with two sites showing approximately equivalent occupancies [0.532 (15) and 0.478 (15)].
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Project description:Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the "lower" aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2',6'-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands.
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Project description:[Cp*Rh] complexes (Cp* = η 5-pentamethylcyclopentadienyl) supported by bidentate chelating ligands are useful in studies of redox chemistry and catalysis, but little information is available for derivatives bearing "hybrid" [P,N] chelates. Here, the preparation, structural characterization, and chemical and electrochemical properties of a [Cp*Rh] complex bearing the κ2-[P,N]-2-[(diphenylphosphino)methyl]pyridine ligand (PN) are reported. Cyclic voltammetry data reveal that [Cp*Rh(PN)Cl]PF6 (1) undergoes a chemically reversible, net two-electron reduction at -1.28 V vs. ferrocenium/ferrocene, resulting in generation of a rhodium(I) complex (3) that is stable on the timescale of the voltammetry. However, 1H and 31P{1H} NMR studies reveal that chemical reduction of 1 generates a mixture of products over a 1 h timescale; this mixture forms as a result of deprotonation of the methylene group of 1 by 3 followed by further reactivity. The analogous complex [Cp*Rh(PQN)Cl]PF6 (2; PQN = κ2-[P,N]-8-(diphenylphosphino)quinoline) does not undergo self-deprotonation or further reactivity upon two-electron reduction, confirming the reactivity of the acidic backbone methylene C-H bonds in the PN complexes. Comparison of the electrochemical properties 1 and 2 also shows that the extended conjugated system of PQN contributes to an additional ligand-centered redox event for 2 that is absent for 1.
| S-EPMC7413167 | biostudies-literature