Synthesis, NMR studies, and molecular orbital calculations on cyclohexadienyl derivatives of (η6-arene)tris(pyrazolyl)ruthenium(II) compounds

Bhambri, Sameer; Bishop, A. W.; Kaltsoyannis, Nikolas; Tocher, Derek A.

doi:10.1039/a804254c

Cited by 34 publications

(14 citation statements)

References 21 publications

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“…Experimental and theoretical investigations have shown the rotational energetic barrier of arene ligands in organometallic complexes to be very low (∼0.5 kcal/mol [(η 6 -benzene)Cr(CO) 3 ], ∼2.5 kcal/mol in [(η 6 -C 6 H 6 )Ru{κ 3 -HB(pz) 3 }] + ). [34][35][36] In our CPMD simulations we observed even at temperatures lower than 310 K a full rotation of the benzene ligand in [(η 6 -C 6 H 6 )Ru(en)(N7{G})] 2+ (4) on the ps time scale. There seemed to be no effective rotational barrier for rotation at temperatures higher than 150 K. Using DFT and the BP86 functional, we calculated a rotational energy barrier in [(η 6 -C 6 H 6 )Ru(en)(Cl)] + (3) of 0.17 kcal/ mol in correspondence with the rotated geometry in Figure 2.…”

Section: Resultsmentioning

confidence: 92%

Structural and Energetic Properties of Organometallic Ruthenium(II) Diamine Anticancer Compounds and Their Interaction with Nucleobases

Gossens

Tavernelli

Röthlisberger

2007

J. Chem. Theory Comput.

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We rationalize the chemoselectivity of the monofunctional ruthenium anticancer compound [(η(6)-arene)Ru(II)(en)(OH2)](2+) (en=ethylenediamine; arene=benzene 1, p-cymene 2) toward guanine, using static DFT (BP86) and MP2 calculations together with Car-Parrinello molecular dynamics. The calculated binding energies for the three investigated nucleobases (G, A, C) decreases in the order G(N7) ≫ C(O2) ∼ C(N3) > A(N7) > G(O6) > OH2. The G(N7) complex is the most stable product due to a hydrogen bond of its O6 with one of the H2N-amine groups of en, while the corresponding NH2-H2N(en) interaction in the adenine complex is repulsive. A very low rotational barrier of 0.17 kcal/mol (BP86) and 0.64 kcal/mol (MP2) was calculated for the arene rotation in [(η(6)-C6H6)Ru(en)(Cl)](+) (3) allowing complexes containing arenes with bulky side chains like p-cymene to minimize steric interactions with, e.g., DNA by simple arene rotation. All [(η(6)-arene)Ru(en)(L)](2+) compounds exist in two stable conformers obtained for different diamine dihedral angle (NCCN) orientation, which, in the case of asymmetric ligands L, differ by up to ∼2.8 kcal/mol. Car-Parrinello dynamics reveal a chelating transition state for the interconversion between N7 and O6 binding of guanine to [(η(6)-arene)Ru(en)](2+).

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Section: Resultsmentioning

confidence: 92%

Structural and Energetic Properties of Organometallic Ruthenium(II) Diamine Anticancer Compounds and Their Interaction with Nucleobases

Gossens

Tavernelli

Röthlisberger

2007

J. Chem. Theory Comput.

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“…In the crystal packing of (1)eRh(2) 7.823(3), Rh (1)eCl(4) 2.389(2), Rh (1)eN(1) 2.089(6), Rh (1)eN(2) 2.139(6), Rh (2)eN(4) 2.152(6), Rh (2)eCl(1) 2.393(2), Rh (2)eCl(2) 2.428(2), N(2)eN (3) 1.406(8); N(1)eRh (1)eN(2) 75.8(2), N(1)eRh (1)eCl(4) 88.60 (18), N(2)eRh (1)eCl(4) 88.57 (16), N(4)eRh (2)eCl(1) 88.34 (18), N(4)eRh (2)eCl(2) 85.88(17), Cl (1)eRh (2)eCl (2) 91.45(9). (1)eN(2) 76.98 (14), N(1)eRh (1)eCl (1) 87.67 (10), N(2)eRh (1)eCl (1) 93.81 (9), N(4)eRh (2)eCl (2) 87.54 (10), N(4)eRh (2)eO(2) 76.43(13), Cl (2)eRh (2)eO(2) …”

Section: Resultsmentioning

confidence: 99%

Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands

Gupta

Gloria

Nongbri

et al. 2011

Journal of Organometallic Chemistry

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Keywords Arene ligands Pyridine aldehydes Schiff bases Ruthenium Rhodium and iridium a b s t r a c tA series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (L1) and ((picolinamido)phenyl) picolinamide (L2) ligands: , 9; Ir, 10). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives 4, 6 and 9 has been determined by Xray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand L2, both ruthenium centers having h 6 -arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with h 5 -Cp* groups are bonded to the ligand N,O and N,N fashion.

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“…Arene ruthenium compounds have also been extensively investigated for their persuasive antibacterial and anticancer activity [10,11]. The arene confers great stability to ruthenium in the +2 oxidation state and the characteristic ''piano stool" structure offers the possibility to vary the additional donors via substitution of halide(s) with a variety of r-donors ranging from tertiary phosphines [12] to b-diketones [13] to aliphatic as well as aromatic amines [14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two pyrazolyl-pyridine units linked by an aromatic spacer

Gupta

Therrien

Rao

2010

Journal of Organometallic Chemistry

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a b s t r a c tReaction of the bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN\NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(g 6 -arene) 2 Ru 2 (NN\NN)Cl 2 ] 2+ (arene = C 6 H 6 , 1; p-i PrC 6 H 4 Me, 2; C 6 Me 6 , 3), [(g 5 -C 5 Me 5 ) 2 M 2 (NN\NN)Cl 2 ] 2+ (M = Rh, 4; Ir, 5), [(g 5 -C 5 H 5 ) 2 M 2 (NN\NN)(PPh 3 ) 2 ] 2+ (M = Ru, 6; Os, 7), [(g 5 -C 5 Me 5 ) 2 Ru 2 (NN\NN)(PPh 3 ) 2 ] 2+ (8) and [(g 5 -C 9 H 7 ) 2 Ru 2 (NN\NN)(PPh 3 ) 2 ] 2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF 6 ] 2 , [4][PF 6 ] 2 and [6][PF 6 ] 2 , has been determined by X-ray crystallographic studies.

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Synthesis, NMR studies, and molecular orbital calculations on cyclohexadienyl derivatives of (η6-arene)tris(pyrazolyl)ruthenium(II) compounds

Cited by 34 publications

References 21 publications

Structural and Energetic Properties of Organometallic Ruthenium(II) Diamine Anticancer Compounds and Their Interaction with Nucleobases

Structural and Energetic Properties of Organometallic Ruthenium(II) Diamine Anticancer Compounds and Their Interaction with Nucleobases

Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands

Half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two pyrazolyl-pyridine units linked by an aromatic spacer

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