Structure and Dynamics of Half-Sandwich Ruthenium(IV) Alkynyl Hydrido Complexes (original) (raw)
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Organometallics, 1997
The chemistry of half-sandwich methyl-substituted indenyl complexes of the late transition metals has been scarcely studied compared to that of the analogous C 5 -Me 5 derivatives. 1 In particular, as far as we are aware, no methylindenyl ruthenium complexes have yet been described, in spite of the potential interest of indenyl complexes based on the enhanced reactivity (generally associated with the indenyl effect) with respect to the analogous cyclopentadienyl derivatives. During the last few years, we have described 2-4 the synthesis of novel ruthenium(II) η 5 -indenyl complexes and have investigated the influence of the indenyl ring in the chemical behavior of unsaturated carbene derivatives. Herein, we report the first ruthenium(II) 1,2,3-trimethylindenyl complexes including alkynyl, alkenyl-carbene, and allenylidene derivatives containing the fragments [Ru-(η 5 -1,2,3-Me 3 C 9 H 4 )LL′] (L ) CO, L′ ) PR 3 ; L-L′ ) bis-(diphenylphosphino)methane (dppm)).
Journal of Organometallic Chemistry 817 (2016) 26-
Solvent effects on the photophysical properties of Bu 4 N[(4,4 0-bpy) Re(CO) 3 (bpy-5,5 0-diCOO)] complex. A combined experimental and computational study a b s t r a c t The photophysical properties of the complex Bu 4 N[(4,4 0-bpy)Re(CO) 3 (bpy-5,5 0-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as 1 MLLCT ReðCOÞ 3 /4;4 0 Àbpy and 1 MLLCT ReðCOÞ 3 /bpyÀ5;5 0 ÀdiCOO. The simulated absorption spectra of the Re(I) complex in H 2 O, protic (EtOH, MeOH) and aprotic (CHCl 3 , CH 2 Cl 2 , CH 3 CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (m) increases with the dielectric constant of the solvent (ε r). Besides, the energy of 1 MLLCT ReðCOÞ 3 /4;4 0 Àbpy also increases with ε r. However, the energy of the 1 MLLCT ReðCOÞ 3 /bpyÀ5;5 0 ÀdiCOO transition is rather insensitive to ε r. This disparity is attributed to the fact that the 1 MLLCT ReðCOÞ 3 /4;4 0 Àbpy transition is nearly parallel to the orientation of m while the 1 MLLCT ReðCOÞ 3 /bpyÀ5;5 0 ÀdiCOO transition is almost perpendicular to it. Unrestricted TD-DFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the ReeN distances are shortened while ReeC distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or D(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of 3 MLLCT ReðCOÞ 3 /4;4 0 Àbpy , 3 MLLCT ReðCOÞ 3 /bpyÀ5;5 0 ÀdiCOO and 1 IL excited states.
Organometallic 1998, 17, 4259-4262.pdf
The crystal structure of di-n-butyltin pyridine-2-phosphonate-6-carboxylate, [C 14 H 24 NO 6 -PSn] 2 , features centrosymmetric dimers disposed about a central Sn 2 O 2 core. The phosphonate carboxylate dianion is µ 2 -tetradentate, coordinating one tin atom via one of the phosphonate oxygen atoms, the pyridine nitrogen atom, and one of the carboxylate oxygen atoms; the latter atom also coordinates the second tin atom of the dimer. The remaining positions in the seven-coordinate, distorted pentagonal bipyramidal geometry are occupied by a water molecule and two n-butyl groups that occupy axial positions. The lattice is stabilized by hydrogen-bonding contacts leading to an arrangement of parallel, orthogonally related chains of dimeric units. In methanol solution, the dimer is involved in a dissociation equilibrium that is fast on the NMR time scale. (1) (a) Gielen, M.; Joosen, E.; Mancilla, T.; Jurkschat, K.; Willem, R.; Roobol, C.; Bernheim, J.; Atassi, G.; Huber, F.; Hoffmann, E.; Preut, H.; Mahieu, B. Main Group Met. Chem. 1987, 10, 147. (b) Gielen, M.; Acheddad, M.; Bouâ lam, M.; Biesemans, M.; Willem, R. Bull. Soc. Chim. Belg. 1991, 100, 743. (c) Gielen, M.; Acheddad, M.; Mahieu, M.; Willem, R. Main Group Met. Chem. 1991, 14, 73. (d) Willem, R.; Biesemans, M.; Bouâ lam, M.; Delmotte, A.; El Khloufi, A.; Gielen, M. Appl. Organomet. Chem. 1993, 7, 311. (2) (a) Huber, F.; Preut, H.; Hoffmann, E.; Gielen, M. Acta Crystallogr. 1989, C45, 51. (b) Gielen, M.; Acheddad, M.; Tiekink, E. R. T.
Vijayan et al 2016 Applied Organometallic Chemistry
N,N-[(diethylamino)(thiocarbonyl)]-substituted benzamidine ligands have been synthesized from the reaction of N,N-[(diethylamino)(thiocarbonyl)]benzimidoyl chloride with functionalized amines such as 2-aminophenol and 2-picolylamine. The reaction of N,N-[(diethylamino)(thiocarbonyl)]-2-hydroxyphenylbenzamidine (H 2 L 1 ) with ruthenium(II) precursor [RuHCl(CO)(PPh 3 ) 3 ] afforded complex 1 of the type [Ru(L 1 )(CO)(PPh 3 ) 2 ] in which the ligand coordinated in tridentate ONS mode. The reaction of H 2 L 1 with copper precursor [Cu(CH 3 COO)(PPh 3 ) 2 ] induced C═N bond cleavage of the ligand and afforded complex 3 of the type [Cu(1,1-DT) (Cl)(PPh 3 ) 2 ]
GunesKurkcuogli Journal of Molecular Structure 2014
Three new cyano-bridged heteronuclear polymeric complexes were synthesized. The complexes are analyzed by FT-IR and Raman spectra. The structures of 2 and 3 were determined by X-ray single crystal diffraction method. The structures of the complexes consist of a 1D zigzag chain. The adjacent 1D layers were extended to a 3D hydrogen-bonded network.
J.Serb.Chem.Soc. 67(12)825–832(2002) UDC 541.89–034:542.913:543.422.25 JSCS–3007
2002
Abstract: Metal complexes of a 20-membered tetraazamacrocycle 2,12-dimethyl-3,13-di-n-propyl-1,4,11,14-tetraazacycloeicosa-1,3,11,13-tetraene (L) of the type [MLX2]X (M = Cr(III), Fe(III); X=NO3) [CoLNO3]NO3, [NiL(NO3) 2], [CuL]Cl2 and [ZnLCl2] have been prepared by2+2 cyclocondensation of 2,3-hexanedione with 1,6-diaminohexane in the presence of metal ions as templates. These complexes were characterized by elemental analyses, conductances, IR and electronic spectra and magnetic measurements.
6.10a. Inorg. Chem. 31,1233.pdf
The ruthenium complex [Ru2(CloHsN2)(CO),(PiPr3),] (1) (CloHIoN2 = 1,8-diaminonaphthalene) reacts with 1 equiv of HgX, (X = C1, Br, I, 02CCH,, 02CPh, 02CCH2C1, 02CCF3, SCN, ONC) to give the adducts [(1)HgX2], in which the Hg atoms are bonded to both Ru atoms of complex 1. Correlations between the 2J(3'P-199Hg) coupling constants of their 31P NMR spectra and the corresponding halogen electronegativities or acid pK,s have been observed. With the exception of [(1)Hg(O2CCF,),], which does not react with any other mercury(I1) salt, the compounds [(l)HgX,] react with HgX', (X' = C1, Br, I, 02CCH3, 02CPh, 02CCH2C1) to give the insertion products [(l)Hg(p-X'),HgX,] only when X' is more electron-withdrawing than X; otherwise, the addition products [(l)Hg(pX),HgX',] are formed. All reactions of [(l)HgX,] with Hg(02CCF3), give the same substitution product [(l)Hg(02CCF3)2]. The molecular structures of [(l)Hg(O,CCF,),] and [(l)Hg(p-Cl),HgCI,] have been confirmed by X-ray crystallography. [(l)Hg(O,CCF,),]: monoclinic, space group C2/c, a = 23.730 (9) A, b = 12.578 (4) A, c = 14.51 1 (7) A, fl = 94.76 (5)O, Z = 4. [(1)Hg(p-C1),HgC1,]~CH2Cl2: monoclinic, space group P 2 , / n , a = 15.840 (7) A, b = 12.694 (4) A, c = 23.366 (2) A, fl = 105.74 (2)O, Z = 4. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Garda-Granda, S.; Van Der Maelen, J. F. Inorg. Chim. Acta 1991, 185, 187. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Pellinghelli, M. A.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1991, 371. Andreu, P. L.; Cabeza, J. A.; Riera, V.; Robert, F.; Jeannin, Y. J. Organomet. Chem. 1989, 372, C15. Oro, L. A.; Fernindez, M. J.; Modrego, J.; Foces-Foces, C.; Cano, F. H. Angew. Chem., Inr. Ed. Engl. 1984, 23, 913. Fernindez, M. J.; Modrego, J.; Oro, L. A.; Apreda, M. C.; Cano, F. H.; Foces-Foces, C. J. Chem. SOC., Dalton Trans. 1989, 1249. See, for example: Panizo, M.; Cano, M. J. Organomet. Chem. 1984, 266,247. Pardo, M. P.; Cano, M. J. Organomet. Chem. 1983,247,293. Faraone, F.; Lo Schiavo, S.; Bruno, G.; Bombieri, G. J. Chem. Soc., Chem. Commun. 1984, 6. (a) Ermer, S.; King, K.; Rosenberg, E.; Manotti-Lanfredi, A. M.; Tiripicchio, A.; Tiripicchio-Camellini, M. Inorg. Chem. 1983, 22, 1339. (b) Rosenberg, E.; Ryckman, D.; Hsu, I.-N.; Gellert, R. W. Inorg. Chem. 1986, 25, 194. (c) Rosenberg, E.; Hardcastle, K. I.; Day, M. W.; Gobetto, R.; Hajela, S.; Muftikian, R. Organometallics 1991, 10, 203. (d) Fadel, S.; Deutcher, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1977, 16, 704. (e) Fajardo, M.; Holden, H. D.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R. J. Chem. SOC., Chem. Commun., 1984, 24. (f) G6mez-Sa1, M. P.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Syed-Mustaffa, S. N. A. B.
Inorg. Chem. Front., 2015,.pdf
A potential tetradentate monoanionic N 2 O 2 chelator, HL, derived from the condensation of o-vanillin and N,N-dimethylethylenediammine, has been reacted with nickel perchlorate and sodium azide to yield the dinuclear Ni(II) complex [Ni(L)(μ 1,1 -N 3 )Ni(L)(OH 2 ) 2 ]·ClO 4 (1), where L = Me 2 N(CH 2 ) 2 NvCH-C 6 H 3 (O − )-(OCH 3 ). The complex has been characterized by X-ray diffraction analysis and different spectroscopic techniques. The coordination geometry around the Ni(II) centres is a distorted octahedron, with the azide ligand and the phenolato oxygen atom bridging in μ 1,1 and μ 2 mode, respectively. The EPR spectra, recorded at liquid nitrogen temperature (77 K) and room temperature ), show g factors of 2.080 and 2.085, in agreement with the structure determined by X-ray diffraction analysis. The VTM study confirms that there are ferromagnetic interactions between the bridging binuclear Ni(II) ions (S = 1). The evaluation of cytotoxic effects on different human cancer cell lines (A-549, MCF-7 and CaCo-2) suggests that both the ligand and complex 1 have potential anticancer properties. Furthermore, they also exhibit anti-mycobacterial activity against M. tuberculosis H37Rv (ATCC 27294) and M. tuberculosis H37Ra (ATCC 25177) strains. Molecular docking of HL with the enoyl acyl carrier protein reductase of M. tuberculosis H37R v (PDB ID: 4U0K) has been examined, showing that HL forms two hydrogen bonds with Lys165 (1.94 and 2.53 Å) in its best docked pose. † Electronic supplementary information (ESI) available. CCDC 894363. For ESI and crystallographic data in CIF or other electronic format see