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Synthesis and Characterization of Tantalum-Based Early-Late Heterobimetallic Complexes Supported by 2-(diphenylphosphino)pyrrolide Ligands.

ABSTRACT: The synthesis of the metalloligand Ta(κ²-NP)₃Cl₂ (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ²-NP)₃Cl₂ with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl₂Ta(μ₂-NP)₃M (M = Ni (2), Pd (3)) or Cl₂Ta(μ₂-NP)₃MCl (M = Rh (4), Ir (5)). Each pair of complexes is isostructural and contains three phosphinopyrrolide ligands that bridge the metal centers. The d¹⁰ or d⁸ complexes are all diamagnetic and X-ray crystallographic analysis reveals similarly short metal-metal distances, ranging from 2.2979(5) Å to 2.4366(2) Å. Despite the similar bonding metrics in 2-5, treatment with an L type donor (2,6-dimethylphenylisocyanide (CNXylyl)) reveals 3 different coordination geometries in TaNi(CNXylyl) (6), TaPd(CNXylyl) (7), and TaIr(CNXylyl) (8). While complexes 6, 7, and 8 all bind the isocyanide at the late metal, ligand rearrangements are observed in the first row complex 6. Complex 7 binds the isocyanide in the axial position while equatorial binding is observed in 8. All isocyanide adducts maintain close metal-metal contacts in the solid state.

SUBMITTER: Dunn PL

PROVIDER: S-EPMC7156031 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Synthesis of Pyridylimido Complexes of Tantalum and Niobium by Reductive Cleavage of the N═N Bond of 2,2'-Azopyridine: Precursors for Early-Late Heterobimetallic Complexes.

Project description:We report the syntheses of 2-pyridylimido complexes of tantalum and niobium by N═N bond cleavage of 2,2'-azopyridine. Reaction of MCl5 (M = Ta and Nb) with 2,2'-azopyridine in the presence of 0.5 equiv of 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (abbreviated Si-Me-CHD) afforded a dark red solution (for Ta) and a dark blue solution (for Nb) with some insoluble precipitates. After removing the solids, another 0.5 equiv of Si-Me-CHD was added to each solution, giving [M(═Npy)Cl3]n (1a: M = Ta; 1b: M = Nb) through reductive cleavage of the N═N bond of 2,2'-azopyridine. The initial products of the above reactions were determined to be 2,2'-azopyridine-bridged dinuclear complexes, [(MCl4)2(μ-pyNNpy)] (2a: M = Ta; 2b: M = Nb), which were isolated by treating MCl5 with 2,2'-azopyridine and Si-Me-CHD in a 2:1:1 molar ratio. In 2a and 2b, the N═N bond was reduced to a single bond via two-electron reduction. Further reduction of complexes 2a and 2b with 1 equiv of Si-Me-CHD afforded complexes 1a and 1b. An anionic doubly μ-imido-bridged ditantalum complex, [nBu4N][Ta2(μ-Npy)2Cl7] (3a), was generated upon addition of nBu4NCl to complex 1a, while addition of nBu4NCl to niobium complex 1b gave a polymeric terminal imido complex, [nBu4N]n/2[{Nb(═Npy)Cl3}2(μ-Cl)]n/2 (3b). Complexations of 1a and 1b with 1 equiv of 2,2'-bipyridine resulted in the formation of mononuclear 2-pyridylimido complexes, M(═Npy)Cl3(bipy) (4a: M = Ta; 4b: M = Nb), whose main structural feature is intramolecular hydrogen bonding between the ortho hydrogen atom of 2,2'-bipyridine and the nitrogen atom of the pyridyl group on the imido ligand. Isolated 2-pyridylimido complexes 4a and 4b reacted with [RhCl(cod)]2 to produce the corresponding early-late heterobimetallic complexes, (bipy)MCl3(μ-Npy)RhCl(cod) (5a: M = Ta; 5b: M = Nb).

| S-EPMC7017918 | biostudies-literature

Synthesis and structural characterization of rhenium(I) tricarbonyl complexes with the bidentate ligands o-(diphenylphosphino)benzaldehyde (P∩O) and o-[(diphenylphosphino)benzylidene]analine (P∩N).

Project description:A series of rhenium(I) tricarbonyl complexes with bidentate P,O donor ligand o-(diphenylphosphino)benzaldehyde (P∩O) and its Schiff base P,N donor ligand o-[diphenylphosphino)benzylidene]analine (P∩N) have been synthesized and structurally characterized. All the complexes of the type [ReX(CO)(3)(LL)] (where LL = P∩O, P∩N) reveal a distorted octahedral structure with the three carbonyl ligands arranged in the facial fashion. Crystal data for 1, C(22)H(15)ClO(4)PRe·1/2C(6)H(14): triclinic, P1, a=8.7430(4), b=9.5767(4), c=13.9449(6) Å, α=93.651(1), β=101.265(1), γ=93.048(1); V=1140.20(9) Å(3), Z=2.2, C(22)H(15)BrO(4)Pre: monoclinic, C2/c, a=31.6800(16), b=8.8880(4), c=18.4517(9) Å, β=124.990(1); V=4256.4(4) Å(3), Z=8. 3, C(28)H(20)ClNO(3)Pre: monoclinic, C2/c, a=22.675(4), b=8.803(2), c=28.218(5) Å, β=100.192(3); V=5543.5(16) Å(3), Z=8.4, C(28)H(20)BrNO(3)Pre: monoclinic, C2/c, a=23.035(1), b=8.7561(4), c=28.269(1) Å, β=100.811(1); V=5600.4(5) Å(3), Z=8.

| S-EPMC3098572 | biostudies-literature

Silylamido supported dinitrogen heterobimetallic complexes: syntheses and their catalytic ability.

Project description:Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(Me3Si)N]3MoN2Mg(THF)2[N(SiMe3)Ar] (5) and [Ar(Me3Si)N]3MoN2SiMe3 (6) (Ar = 3,5-Me2C6H3) were synthesized and structurally characterized, and proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. The 1H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating possible catalytic ability of the Mo-N=N motif.

| S-EPMC8694672 | biostudies-literature

Heterobimetallic Coinage Metal-Ruthenium Complexes Supported by Anionic N-Heterocyclic Carbenes.

Project description:The lithium complexes [(WCA-NHC)Li(toluene)] of anionic N-heterocyclic carbenes with a weakly coordinating borate moiety (WCA-NHC, WCA=B(C6 F5 )3 , NHC=IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were used for the preparation of silver(I) or copper(I) WCA-NHC complexes. While the reactions in THF with AgCl or CuCl afforded anionic mono- and dicarbene complexes with solvated lithium counterions [Li(THF)n ]+ (n=3, 4), the reactions in toluene proceeded with elimination of LiCl and formation of the neutral phosphine and arene complexes [(WCA-NHC)M(PPh3 )] and [(WCA-NHC)M(η2 -toluene)] (M=Ag, Cu). The latter were used for the preparation of chlorido- and iodido-bridged heterobimetallic Ag/Ru and Cu/Ru complexes [(WCA-NHC)M(μ-X)2 Ru(PPh3 )(η6 -p-cymene)] (M=Ag, Cu, X=Cl; M=Ag, X=I). Surprisingly, these complexes resisted the elimination of CuCl, AgCl, or AgI, precluding WCA-NHC transmetalation.

| S-EPMC8597159 | biostudies-literature

Synthesis, properties, and catalysis of p-block complexes supported by bis(arylimino)acenaphthene ligands.

Project description:Bis(arylimino)acenaphthene (Ar-BIAN) ligands have been recognized as robust scaffolds for metal complexes since the 1990 s and most of their coordination chemistry was developed with transition metals. Notably, there have been relatively few reports on complexes comprising main group elements, especially those capitalizing on the redox non-innocence of Ar-BIAN ligands supporting p-block elements. Here we present an overview of synthetic approaches to Ar-BIAN ligands and their p-block complexes using conventional solution-based methodologies and environmentally-benign mechanochemical routes. This is followed by a discussion on their catalytic properties, including comparisons to transition metal counterparts, as well as key structural and electronic properties of p-block Ar-BIAN complexes.

| S-EPMC9814787 | biostudies-literature

Investigating the Ring-Opening Polymerization Activity of Niobium and Tantalum Ethoxides Supported by Phenoxyimine Ligands.

Project description:A variety of metal catalysts from around the periodic table have been studied for the ring-opening polymerization (ROP) of cyclic esters. Within this field, group V catalysts have been rarely explored. To better understand the effect the choice of metal and ligand has on ROP activity, a series of 10 niobium and tantalum alkoxide catalysts, supported by a range of phenoxyimine ligands, were synthesized. The electronics and steric bulk of the ligands were varied on the phenoxy group ( t Bu, Cl, and OMe) and the imine group (Ph; 2,6-diMePh; 2,6-di i PrPh; and 2,4,6-tri t BuPh) to probe their effect on the catalyst structure and activity. Catalysts were characterized with 1D, 2D, and variable-temperature NMR techniques to determine their structure in solution. Single crystal X-ray diffraction studies were conducted to establish their solid-state structure. The 10 catalysts are pseudo-octahedral, and each shows ligand coordination through phenoxy-oxygen and imine-nitrogen (O,N). In the case of the o-vanillin ligand set, however, evidence was found for O,O-coordination of the ligand when the steric encumbrance of the imine-nitrogen was increased. Each catalyst was active for the ring-opening polymerization of both rac-lactide (LA) and ε-caprolactone (CL) in the absence of solvent at 140 °C. In the case of CL, the catalysts supported by chloro-containing ligands showed the most polymerization control based on final polymer molecular weight and dispersity. Ligand trends were less clear for the polymerization of LA, though in all cases the catalysts were more controlled than the parent homoleptic alkoxide [M(OEt)5; M = Nb or Ta]. The most promising catalyst in the family was tested for copolymerization activity of LA and CL in one pot. Copolymerization of the two monomers was successful and yielded random poly(caprolactone-co-lactide).

| S-EPMC9281319 | biostudies-literature

Synthesis, Characterization, and Catalytic Activity of Ni(II) Alkyl Complexes Supported by Pyrrole-Diphosphine Ligands.

Project description:The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P2RPyr)- (P2RPyr = 2,5-(R2PCH2)2C4H2N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P2R Pyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square planar geometries about nickel. The hydride complex, [NiH(P2CyPyr)], can also prepared either through treatment of [NiCl(P2CyPyr)] with LiHBEt3, or by reaction of H(P2RPyr) with [Ni(COD)2] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO2, respectively, evince clean migratory insertion chemistry of the Ni-C and Ni-H bonds. Both the alkyl and chloride complexes are active catalysts for the Kumada coupling of aryl chlorides and aryl or alkyl Grignard reagents at room temperature. The solid-state structures of several of the complexes are reported.

| S-EPMC3931010 | biostudies-literature

Stepwise assembly of heterobimetallic complexes: synthesis, structure, and physical properties.

Project description:Bimetallic active sites are ubiquitous in metalloenzymes and have sparked investigations of synthetic models to aid in the establishment of structure-function relationship. We previously reported a series of discrete bimetallic complexes with [FeIII-(μ-OH)-MII] cores in which the ligand framework provides distinct binding sites for two metal centers. The formation of these complexes relied on a stepwise synthetic approach in which an FeIII-OH complex containing a sulfonamido tripodal ligand served as a synthon that promoted assembly. We have utilized this approach in the present study to produce a new series of bimetallic complexes with [FeIII-(μ-OH)-MII] cores (M = Ni, Cu, Zn) by using an ancillary ligand to the FeIII center that contains phosphinic amido groups. Assembly began with formation of an FeIII-OH that was subsequently used to bind the MII fragment that contained a triazacyclononane ligand. The series of bimetallic complexes were charactered structurally by X-ray diffraction methods, spectroscopically by absorption, vibrational, electron paramagnetic resonance spectroscopies, and electrochemically by cyclic voltammetry. A notable finding is that these new [FeIII-(μ-OH)-MII] complexes displayed significantly lower reduction potentials than their sulfonamido counterparts, which paves way for future studies on high valent bimetallic complexes in this scaffold.

| S-EPMC8418555 | biostudies-literature

MM Quadruply Bonded Complexes Supported by Vinylbenzoate Ligands: Synthesis, Characterization, Photophysical Properties and Application as Synthons.

Project description:From the reactions between M2(T i PB)4 compounds and meta and para - vinylbenzoic acids (2 equiv) in toluene at room temperature the compounds trans-M2(T i PB)2L2, where L = m-vinylbenzoate 1A (M = Mo) and 1B (M = W) and T i PB = 2,4,6-triisopropylbenzoate, and where L = p-vinylbenzoate 2A (M = Mo) and 2B (M = W) have been isolated. Compounds 1A and 2A have been shown to undergo Heck carbon-carbon coupling reactions with phenyliodide to produce trans-Mo2(T i PB)2(O2CC6H4-m-CH=CH-C6H5)2,3A and trans-Mo2(T i PB)2(O2CC6H4-p-CH=CH-C6H5)2, 4A. The molybdenum compounds 1A and 2A have been structurally characterized by single crystal X-ray crystallography. All the new compounds have been characterized by 1H NMR, IR, UV-Visible absorption and emission spectroscopy, high resolution MALDITOF MS, fs- and ns- transient absorption spectroscopy and fs- time-resolved IR spectroscopy. Electronic structure calculations employing density functional theory, DFT, and time-dependent DFT have been employed to aid in the interpretation of spectral data. All compounds show intense absorptions in the visible region corresponding to M2δ to Lπ* charge transfer transitions. The lifetimes of the 1MLCT state fall in the range of 1 - 10 ps and for the molybdenum complexes the T1 states are 3δδ* with lifetimes ~50 μs while for the tungsten complexes the T1 are 3 MLCT with lifetimes in the range of 3 - 10 ns.

| S-EPMC4583209 | biostudies-literature

Alkali Metal Complexes of a Bis(diphenylphosphino)methane Functionalized Amidinate Ligand: Synthesis and Luminescence.

Project description:A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM-C(N-Dipp)2 H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM-C(N-Dipp)2 }(Ln )] (M=Li, Na, K, Rb, Cs; L=thf, Et2 O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh2 CH2 -C(N-Dipp)2 }]6 was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh2 CH2 -C(N-Dipp)2 }]6 metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes.

| S-EPMC8596514 | biostudies-literature

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