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The Diphosphorus Complex [Cp₂Mo₂(CO)₄(η²-P₂)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers.

ABSTRACT: The three-component reaction of the tetrahedral diphosphorus complex [Cp₂Mo₂(CO)₄(η²-P₂)] (1), with Ag[BF₄] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions.

SUBMITTER: Moussa ME

PROVIDER: S-EPMC5101867 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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The Diphosphorus Complex [Cp2Mo2(CO)4(η2-P2)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers.

Moussa Mehdi Elsayed ME Attenberger Bianca B Fleischmann Martin M Schreiner Andrea A Scheer Manfred M

European journal of inorganic chemistry 20160829 28

The three-component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2-P2)] (1), with Ag[BF4] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-org ...[more]

PMID: 27867315

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Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [Cp2Mo2(CO)4(η2-P2)] Complex and Silver(I) Salts.

Project description:The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η2-P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η2-1)2(η1:η1-1)2][TEF]2 (2) dimer and the [Ag2(η1:η1-1)3] n [TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η1:η1-1)2(η1-CH2Cl2)2(η2-C7H8)2][FAl]2 (4) or the [Ag2(η2-1)2(η1:η1-1)2][FAl]2 (5) dimer and the [Ag2(η1:η1-1)4] n [FAl]2n (6) coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure.

| S-EPMC5586200 | biostudies-literature

A Neutral "Aluminocene" Sandwich Complex: η1 - versus η5 -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5 Me5 ).

Project description:The pentaaryl borole (Ph*C)4 BXylF [Ph*=3,5-tBu2 (C6 H3 ); XylF =3,5-(CF3 )2 (C6 H3 )] reacts with low-valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4 , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral η5 -Cp*,η5 -[(Ph*C)4 BXylF ] complex of AlIII revealed a strong, ionic bonding interaction. The formation of the heteroleptic borole-cyclopentadienyl "aluminocene" leads to significant changes in the 13 C NMR chemical shifts within the borole unit. In the case of the less-reductive GaCp*, borole (Ph*C)4 BXylF reacts as a Lewis acid to form a dynamic adduct with a dative 2-center-2-electron Ga-B bond. The Lewis adduct was also studied structurally, spectroscopically, and computationally.

| S-EPMC6856865 | biostudies-literature

Crystal structure of the [(THF)Cs(μ-η5:η5-Cp')3Yb] n oligomer.

Project description:The green compound poly[(tetra-hydro-furan)-tris-[μ-η5:η5-1-(tri-methyl-sil-yl)cyclo-penta-dien-yl]caesium(I)ytterbium(II)], [CsYb(C8H13Si)3(C4H8O)] n or [(THF)Cs(μ-η5:η5-Cp')3YbII] n was synthesized by reduction of a red THF solution of (C5H4SiMe3)3YbIII with excess Cs metal and identified by X-ray diffraction. The compound crystallizes as a two-dimensional array of hexa-gons with alternating CsI and YbII ions at the vertices and cyclo-penta-dienyl groups bridging each edge. This, based off the six-electron cyclo-penta-dienyl rings occupying three coordination positions, gives a formally nine-coordinate tris-(cyclo-penta-dien-yl) coordination environment to Yb and the Cs is ten-coordinate due to the three cyclo-penta-dienyl rings and a coordinated mol-ecule of THF. The complex comprises layers of Cs3Yb3 hexa-gons with THF ligands and Me3Si groups in between the layers. The Yb-C metrical parameters are consistent with a 4f 14 YbII electron configuration.

| S-EPMC7336790 | biostudies-literature

Steric Switching From Photochemical to Thermal N2 Splitting: A Computational Analysis of the Isomerization Reaction {(Cp*)(Am)Mo}2(?-?1:?1-N2) ? {(Cp*)(Am)Mo}2(?-N)2.

Project description:A ?-?1:?1-N2-bridged Mo dimer, {(?5-C5Me5)[N(Et)C(Ph)N(Et)]Mo}2(?-N2), cleaves dinitrogen thermally resulting in a crystallographically characterized bis-?-N-bridged dimer, {(?5-C5Me5)[N(Et)C(Ph)N(Et)]Mo}2(?-N)2. A structurally related Mo dimer with a bulkier amidinate ligand, ([N(iPr)C(Me)N(iPr)]), is only capable of photochemical dinitrogen activation. These opposing reactivities were rationalized as steric switching between the thermally and photochemically active species. A computational analysis of the geometric and electronic structures of intermediates along the isomerization pathway from Mo2(?-?1:?1-N2) to Mo2(?-?2:?1-N2) and Mo2(?-?2:?2-N2), and finally Mo2(?-N)2, is presented here. The extent to which dispersion affects the thermodynamics of the isomers is evaluated, and it is found that dispersion interactions play a significant role in stabilizing the product and making the reaction exergonic. The concept of steric switching is further explored with theoretical models with sterically even less demanding ligands, indicating that systematic ligand modifications could be used to rationally design the N2 activation energy landscape. An analysis of electronic excitations in the computed UV-vis spectra of the two complexes shows that a particular type of asymmetric excitations is only present in the photoactive complex.

| S-EPMC6535493 | biostudies-literature

Mixed Organometallic-Organic Hybrid Assemblies Based on the Diarsene Complex [Cp2 Mo2 (CO)4 (μ,η2 -As2 )], AgI Salts and N-Donor Organic Molecules.

Project description:The reaction of the organometallic diarsene complex [Cp2 Mo2 (CO)4 (η2 -As2 )] (1) with Ag[Al{OC(CF3 )3 }4 ] (Ag[TEF]) yielded the AgI monomer [Ag(η2 -1)3 ][TEF] (2). This compound exhibits dynamic behavior in solution, which allows directed selective synthesis of unprecedented organometallic-organic hybrid assemblies upon its reaction with N-donor organic molecules by a stepwise pathway, which is supported by DFT calculations. Accordingly, the reaction of 2 with 2,2'-bipyrimidine (L1) yielded the dicationic molecular compound [{(η2 -1)2 Ag}2 (μ-L1)][TEF]2 (3) or the 1D polymer [{(η2 -1)Ag}(μ-L1)]n [TEF]n (4) depending on the ratio of the reactants. However, its reactions with the pyridine-based linkers 4,4'-bipyridine (L2), 1,2-bis(4-pyridyl)ethylene (L3) and 1,2-bis(4-pyridyl)ethyne (L4) allowed the formation of the 2D polymers [{(η2 -1)Ag}2 (μ-Lx)3 ]n [TEF]2n [Lx=L2 (5), L3 (6), L4 (7), respectively]. Additionally, this concept was extended to step-by-step one-pot reactions of 1, [Ag(CH3 CN)3 ][Al{OC(CF3 )2 (CCl3 )}4 ] ([Ag(CH3 CN)3 ][TEFCl ]) and linkers L2-L4 to produce the 2D polymers [{(η2 -1)Ag}2 (μ,Lx)3 ]n [TEFCl ]2n [Lx=L2 (8), L3 (9), L4 (10), respectively].

| S-EPMC7986401 | biostudies-literature

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] Towards the "Naked" Cations Cu(+) , Ag(+) , and Tl(.).

Project description:Although the cyclo-P6 complex [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the "naked" cations Cu(+) , Ag(+) , and Tl(+) . Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2 ](+) complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M(+) cations. The choice of solvent enabled control over the reaction outcome for Cu(+) , as proved by powder XRD and supported by DFT calculations. The reaction with Tl(+) affords a layered two-dimensional coordination network in the solid state.

| S-EPMC4675074 | biostudies-literature

Transformations of the cyclo-P4 ligand in [Cp'''Co(η4-P4)].

Project description:The reactivity of the cyclo-P4 ligand complex [Cp'''Co(η4-P4)] (1) (Cp''' = 1,2,4-tri-tert-butyl-cyclopentadienyl) towards reduction and main group nucleophiles was investigated. By using K[CpFe(CO)2], a selective reduction to the dianionic complex [(Cp'''Co)2(μ,η3:η3-P8)]2- (2) was achieved. The reaction of 1 with t BuLi and LiCH2SiMe3 as carbon-based nucleophiles yielded [Cp'''Co(η3-P4R)]- (R = t Bu (4), CH2SiMe3 (7)), which, depending on the reaction conditions, undergo subsequent reactions with another equivalent of 1 to form [(Cp'''Co)2(μ,η3:η3-P8R)]- (R = t Bu (5), CH2SiMe3 (8)). In the case of 4, a different pathway was observed, namely a dimerisation followed by a fragmentation into [Cp'''Co(η3-P5 t Bu2)]- (6) and [Cp'''Co(η3-P3)]- (3). With OH- as an oxygen-based nucleophile, the synthesis of [Cp'''Co(η3-P4(O)H)]- (9) was achieved. All compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy and mass spectrometry. Their electronic structures and reaction behavior were elucidated by DFT calculations.

| S-EPMC8159306 | biostudies-literature

A New Systematic Construction of Novel Three-Dimensional Spin Crossover Coordination Polymers Based on the [AgI 2(CN)3] Building Unit.

Project description:New three-dimensional spin crossover (SCO) coordination polymers systematically constructed by the novel building unit [AgI 2(CN)3], FeII(3-Br-5-CH3pyridine)2[AgI 2(CN)3][AgI(CN)2] (1), FeII(3-Br-5-Clpyridine)2[AgI 2(CN)3][AgI(CN)2] (2), and FeII(3,5-Brpyridine)2[AgI 2(CN)3][AgI(CN)2] (3), have been synthesized and characterized. The bismonodentate binuclear [Ag2(CN)3]- and mononuclear [AgI(CN)2]- units and FeII atoms assemble to form a 3D network structure. The structures of 1-3 are crystallographically identical, which made up the triply interpenetration combined with complicated intermolecular interactions including Ag···Ag, Ag···X (pyridine substituents) and π-stacking interactions. Magnetic and differential scanning calorimetry studies were performed for 1-3. These compounds display a similar SCO behavior, while the critical temperatures (T c) are shifted by the substituent effect. Due to the identical structures of 1-3, the order of T c clearly corresponds with the Hammett constant.

| S-EPMC8154166 | biostudies-literature

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp2Zr(η5,η1-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.

Project description:The crystal structure of a solvated zirconocene penta-fulvene complex with a bulky adamantyl-idene substitution pattern, namely (η5,η1-adamantyl-idene-penta-fulvene)bis-(η5-cyclo-penta-dien-yl)zirconium(IV)-toluene-n-hexane (8/1/1), [Zr(C15H18)(C5H5)2]·0.125C7H8·0.125C6H14, is reported. Reducing zirconocene dichloride with magnesium results in the formation of a low-valent zirconocene reagent that reacts readily with adamantyl-idene-penta-fulvene to give the aforementioned complex. Single crystal X-ray diffraction proves the dianion-like η5:η1 binding mode of the fulvene ligand to the central ZrIV atom. The asymmetric unit contains four independent mol-ecules of [η5:η1-adamantyl-idene-penta-fulvene]bis-[(η5)-cyclo-penta-dien-yl]zirconium(IV), together with half a mol-ecule of toluene disordered with half a mol-ecule of n-hexane (the solvent mol-ecules have no direct influence on the complex). In each of the four complex mol-ecules, the central ZrIV atom has a distorted tetra-hedral coordination environment. The measured crystal consisted of two domains with a refined ratio of 0.77:0.23.

| S-EPMC5730232 | biostudies-literature

Coordination Chemistry of P4 S3 and P4 Se3 towards the Iron Fragments [Fe(Cp)(CO)2 ]+ and [Fe(Cp)(PPh3 )(CO)].

Project description:The complexes Ag(L)n [WCA] (L=P4 S3 , P4 Se3 , As4 S3 , and As4 S4 ; [WCA]=[Al(ORF )4 ]- and [F{Al(ORF )3 }2 ]- ; RF =C(CF3 )3 ; WCA=weakly coordinating anion) were tested for their performance as ligand-transfer reagents to transfer the poorly soluble nortricyclane cages P4 S3 , P4 Se3 , and As4 S3 as well as realgar As4 S4 to different transition-metal fragments. As4 S4 and As4 S3 with the poorest solubility did not yield complexes. However, the more soluble silver-coordinated P4 S3 and P4 Se3 cages were transferred to the electron-poor Fp+ moiety ([CpFe(CO)2 ]+ ). Thus, reaction of the silver salt in the presence of the ligand with Fp-Br yielded [Fp-P4 S3 ][Al(ORF )4 ] (1?a), [Fp-P4 S3 ][F(Al(ORF )3 )2 ] (1?b), and [Fp-P4 Se3 ][Al(ORF )4 ] (2). Reactions with P4 S3 also yielded [FpPPh3 -P4 S3 ][Al(ORF )4 ] (3), a complex with the more electron-rich monophosphine-substituted Fp+ analogue [FpPPh3 ]+ ([CpFe(PPh3 )(CO)]+ ). All complex salts were characterized by single-crystal XRD, NMR, Raman, and IR spectroscopy. Interestingly, they show characteristic blueshifts of the vibrational modes of the cage, as well as structural contractions of the cages upon coordination to the Fp/FpPPh3 moieties, which oppose the typically observed cage expansions that lead to redshifts in the spectra. Structure, bonding, and thermodynamics were investigated by DFT calculations, which support the observed cage contractions. Its reason is assigned to ? and ? donation from the slightly P-P and P-E antibonding P4 E3 -cage HOMO (e symmetry) to the metal acceptor fragment.

| S-EPMC6771638 | biostudies-literature