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Rhenium(I)-Based Monocyclic and Bicyclic Phosphine Oxide-Coordinated Supramolecular Complexes.

ABSTRACT: Neutral, flexible ditopic phosphine (P-P) or phosphine oxide (O=P-P=O) donors, rigid anionic bis-chelating oxygen donors, and Re2(CO)10 were used to assemble ten phosphine oxide (P=O)-donor-based neutral monocyclic M2LL'-, bicyclic M4L2L?-, and bicyclic M4LL'2-type supramolecular coordination complexes (SCCs). A soft ditopic phosphine donor was transformed into a hard ditopic phosphine oxide donor, during the formation of the cyclic complexes 1-3, 5-6, and 9-10. Complexes 4, 7, and 8 were obtained using a hard P=O donor ligand. These SCCs were characterized using elemental analysis, FTIR, NMR, and single-crystal X-ray diffraction analysis. The absorption properties of 1-8 were studied using absorption UV-vis spectroscopic methods, and the results were analyzed using theoretical calculations. The results revealed that the neutral P=O donor significantly influenced the photophysical properties by enhancing the absorption coefficient in the visible region.

SUBMITTER: Shankar B

PROVIDER: S-EPMC6640797 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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Rhenium(I)-Based Monocyclic and Bicyclic Phosphine Oxide-Coordinated Supramolecular Complexes.

Shankar Bhaskaran B Arumugam Ramar R Elumalai Palani P Sathiyendiran Malaichamy M

ACS omega 20161004 4

Neutral, flexible ditopic phosphine (P-P) or phosphine oxide (O=P-P=O) donors, rigid anionic bis-chelating oxygen donors, and Re2(CO)10 were used to assemble ten phosphine oxide (P=O)-donor-based neutral monocyclic M2LL'-, bicyclic M4L2L″-, and bicyclic M4LL'2-type supramolecular coordination complexes (SCCs). A soft ditopic phosphine donor was transformed into a hard ditopic phosphine oxide donor, during the formation ...[more]

PMID: 31457144

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Project description:Rhenium(I)tricarbonyl core-based heteroleptic "figure-eight"- and Z-shaped metallocycles (1a-4a) of the general formula fac-[{(CO)3Re(μ-L)Re(CO)3}2(dppz)2] were self-assembled from Re2(CO)10, H2-L (H2-L = 5,8-dihydroxy-1,4-naphthaquinone (H2-dhnq) for 1a; 1,4-dihydroxy-9,10-anthraquinone (H2-dhaq) for 2a; 6,11-dihydroxy-5,12-naphthacenedione (H2-dhnd) for 3a; 2,2'-bisbenzimidazole (H2-bbim) for 4a), and bis(4-((pyrazolyl)methyl)phenylmethane) (dppz) via one-pot coordination-driven synthetic approach. The molecular structures of 1a and 4a were unambiguously confirmed by single-crystal X-ray diffraction (SC-XRD) methods. The metallocycles in the DMSO solution exist as an acyclic dinuclear-DMSO adduct of the general formula fac-[{(CO)3Re(μ-L)Re(CO)3}(DMSO)2] (1b, L = dhnq; 2b, L = dhaq; 3b, L = dhnd; 4b, L = bbim) and dppz, which are in dynamic equilibrium. The dynamic behavior of the rhenium-pyrazolyl bond in the solution state was effectively utilized to transform metallocycles 1a-4a into pyridyl/benzimidazolyl/phosphine donor-based heteroleptic metallocycles and acyclic dinuclear complexes (4-13). These include tetranuclear rectangles fac-[{(CO)3Re(μ-L)Re(CO)3}2(4,4'-bpy)2] (4 and 11, L = dhaq for 4 and bbim for 11), dinuclear metallocycles fac-[{(CO)3Re(μ-L)Re(CO)3}(dpbim)] (5-7 and 12; L = dhnq for 5, dhaq for 6, dhnd for 7, and bbim for 12), and dinuclear acyclic complexes fac-[{(CO)3Re(μ-L)Re(CO)3}(PTA)2] (8-10 and 13; L = dhnq for 8, dhaq for 9, dhnd for 10, and bbim for 13). These transformations were achieved through component-induced supramolecular reactions while treating with competitive ligands 4,4'-bipyridine (4,4'-bpy), bis(4-((1H-benzoimidazole-1-yl)methyl)phenyl)methane (dpbim), and 1,3,5-triaza-7-phosphaadamantane (PTA). The reaction mixture in the solution was analyzed using NMR and electrospray ionization mass spectrometry (ESI-MS) analysis. Additionally, crystal structures of 4, 6, and 13, which were obtained in the mixture of the solutions, were determined, providing unequivocal evidence for the occurrence of supramolecular transformation within the system. The results reveal that the size of the chelating ligand and the pyrazolyl donor angle of the ditopic ligand play crucial roles in determining the resulting solid-state metallacyclic architecture in these synthetic combinations. The dynamic behavior of the rhenium-pyrazolyl bond in the metallocycles can be utilized to transform into other metallocycles and acyclic complexes using suitable competing ligands via ligand-induced supramolecular transformations.

Project description:The excellent π-accepting azodicarboxylic esters adcOR (R = Et, iPr, tBu, Bn (CH2-C6H5) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO)3 complexes [{Re(CO)3Cl}2(µ-adcOR)] and [{Re(CO)3Cl}2(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)3Cl(adcpip)] and [Re(CO)3(PPh3)(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show syn and anti isomers for the dinuclear fac-Re(CO)3 complexes at slightly different energies but they were not distinguishable from experimental IR or UV-Vis absorption spectroscopy. The electrochemistry of the adc complexes showed reduction potentials slightly below 0.0 V vs. the ferrocene/ferrocenium couple. Attempts to generate the radicals [{Re(CO)3Cl}2(µ-adcOR)]•- failed as they are inherently unstable, losing very probably first the Cl- coligand and then rapidly cleaving one [Re(CO)3] fragment. Consequently, we found signals in EPR very probably due to mononuclear radical complexes [Re(CO)3(solv)(adc)]•. The underlying Cl-→solvent exchange was modelled for the mononuclear [Re(CO)3Cl(adcpip)] using DFT calculations and showed a markedly enhanced Re-Cl labilisation for the reduced compared with the neutral complex. Both the easy reduction with potentials ranging roughly from -0.2 to -0.1 V for the adc ligands and the low-energy NIR absorptions in the 700 to 850 nm range place the adc ligands with their lowest-lying π* orbital being localised on the azo function, amongst comparable bridging chelate N^N coordinating ligands with low-lying π* orbitals of central azo, tetrazine or pyrazine functions. Comparative (TD)DFT-calculations on the Re(CO)3Cl complexes of the adcpip ligand using the quite established basis set and functionals M06-2X/def2TZVP/LANL2DZ/CPCM(THF) and the more advanced TPSSh/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) for single-point calculations with BP86/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) optimised geometries showed a markedly better agreement of the latter with the experimental XRD, IR and UV-Vis absorption data.

Project description:2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (mu-TPT)[ReX(CO)(3)](2) (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)(5)] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)(3)(TPT)] (2) (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)(5)]. Crystal data are as follows. 1: monoclinic, P2(1)/c, a = 11.751(1) A, b = 11.376(1) A, c = 15.562(2) A, beta = 103.584(2) degrees, V = 2022.0(4) A(3), Z = 4. 2: monoclinic, P2(1)/c, a = 11.896(1) A, b = 11.396(1) A, c = 15.655(1) A, beta = 104.474(2) degrees, V = 2054.9(3) A(3), Z = 4. 3: triclinic, P1, a = 11.541(2) A, b = 12.119(2) A, c = 13.199(2) A, alpha = 80.377(2) degrees, beta = 76.204(3) degrees, gamma = 66.826(2) degrees, V = 1642.5(4) A(3), Z = 2. Crystals of 4 crystallized from acetone: triclinic, P1, a = 11.586(5) A, b = 12.144(5) A, c = 13.364(6) A, alpha = 80.599(7) degrees, beta = 76.271(8) degrees, gamma = 67.158(8) degrees, V = 1678.0(12) A(3), Z = 2. Crystals of 4' are obtained from CH(2)Cl(2)-pentane solution: monoclinic, C2/c, a = 17.555(4) A, b = 15.277(3) A, c = 13.093(3) A, beta = 111.179(3) degrees, V = 3274.0(12) A(3), Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [mu-C(3)N(3)(OMe)(py)(2)(pyH)][ReX(CO)(3)](2) (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) A, b = 16.602(1) A, c = 14.641(1) A, beta = 116.147(1) degrees, V = 5880.5(8) A(3), Z = 8. 6: monoclinic, C2/c, a = 27.513(3) A, b = 16.740(2) A, c = 14.837(2) A, beta = 116.925(2) degrees, V = 6092.8(10) A(3), Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO(-) on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C(3)N(3) ring. Reaction of TPT with [NEt(4)](2)[ReBr(3)(CO)(3)] in benzene-methanol resulted in an unexpected dinuclear complex 7, with formulation [mu-C(3)N(3)(OMe)(py)(3)][Re(CO)(3)][ReBr(CO)(3)]. The methoxylated TPT ligand functions simultaneously as a tridentate and bidentate ligand with two fac-Re(CO)(3)(+) cores. Crystal data for 7: monoclinic, P2(1)/n, a = 12.114(1) A, b = 14.878(1) A, c = 15.807(1) A, beta = 104.601(1) degrees, V = 2756.9(3) A(3), Z = 4.

Dataset Information

Rhenium(I)-Based Monocyclic and Bicyclic Phosphine Oxide-Coordinated Supramolecular Complexes.

Publications

Rhenium(I)-Based Monocyclic and Bicyclic Phosphine Oxide-Coordinated Supramolecular Complexes.

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