Mono‐ and Dinuclear Complexes of Tricarbonylrhenium(I) with 4‐Methyl‐2,2′‐bipyridine‐4′‐carbonitrile

Ortiz, Juan Hugo Mecchia; Vieyra, Faustino E. Morán; Borsarelli, Claudio D.; Romero, Isabel; Fontrodona, Xavier; Parella, Teodor; Katz, Noemí D. Lis de; Fagalde, Florencia; Katz, Néstor E.

doi:10.1002/ejic.201402160

Cited by 6 publications

(8 citation statements)

References 37 publications

(33 reference statements)

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“…This can be assigned to a carboxyamide stretch, which is most likely a decomposition product from the hydrolysis of the cyano groups. This has also been observed for Re(4-methyl-4′-cyano-2,2′-bipyridine)(CO) 3 Cl …”

Section: Resultssupporting

confidence: 68%

Orientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces

Clark

Rudshteyn

et al. 2016

J. Phys. Chem. C

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Sum frequency generation spectroscopy (SFG) and calculations of SFG spectra based on density functional theory are combined to elucidate the orientation of two Re(R-2,2′-bipyridine)(CO)3Cl (R = 4-cyano or 4,4′-dicyano) electrocatalysts when adsorbed on conductive gold surfaces. We find that the electrocatalysts lean on the Au surface to orient the plane of the bipyridine ligand at 63° relative to the surface normal. While the weak binding of the complexes to the gold surface precluded the ability to perform surface immobilized catalysis, homogeneous electrochemical experiments show that the molecular catalysts are active toward the reduction of CO2 to CO and carbonate in the triply reduced state (TOF of 13.3 and 7.2 s–1 for the doubly and singly substituted complexes, respectively). These findings demonstrate the capabilities of the approach of including rigorous spectroscopic and theoretical methods for revealing the conformation and orientation of CO2 reduction catalysts bound to electrode surfaces, which are critical considerations for redox state transitions and catalytic turnover.

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Section: Resultssupporting

confidence: 68%

Orientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces

Clark

Rudshteyn

et al. 2016

J. Phys. Chem. C

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“…The Re–N(MeCN) distances of ca. 2.13 Å in 2 ·PhMe and 6 ·MeCN are similar to those in fac -[Re I (CO) 3 (MeCN)(mcbpy)]PF 6 ·PhMe (2.138(3) Å) and fac -[Re I (CO) 3 (MeCN)(bpy)]ClO 4 (2.140(3) Å) . These distances are all substantially longer than that in trans -Re I Cl(CO) 2 (bpy)(MeCN) (2.043(4) Å) due to the structural trans effect of the CO ligand on the competing π-acceptor MeCN .…”

Section: Results and Discussionmentioning

confidence: 52%

“…The corresponding angle in fac -[Re I (CO) 3 (MeCN)(mcbpy)]PF 6 ·PhMe reported by Mecchia Ortiz et al is similar at ca. 175.9°, while a value of ca. 175.5° is found in fac -[Re I (CO) 3 (MeCN)(bpy)]ClO 4 .…”

Section: Results and Discussionmentioning

confidence: 95%

“…It is worth noting that attempts to prepare a related trimetallic complex from 1 incorporating the dcbpy ligand afforded significant contamination by the bimetallic complex, which could not be removed satisfactorily via chromatography or reprecipitation . However, Mecchia Ortiz et al have used the ligand 4-methyl-4′-cyano-2,2′-bipyridyl (mcbpy) to prepare a heterobimetallic complex featuring fac -{Re I (CO) 3 (MeCN)} + and {Ru II (NH 3 ) 5 } 2+ centers …”

Section: Results and Discussionmentioning

confidence: 99%

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Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores

et al. 2016

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The compounds 4,4′-dicyano-2,2′-bipyridyl (dcbpy), 4,4′-bis(4-cyanophenyl)-2,2′-bipyridyl (bcpbpy), 4,4′-bis[(E)-2-(4-cyanophenyl)vinyl]-2,2′-bipyridyl (bcpvbpy), and 4,4′-bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridyl (bpvbpy) are used to prepare nine new complexes with fac-{ReI(CO)3(L)} n+ (L = Cl–, MeCN, pyridine (py), or 4-cyanopyridine (cpy)) centers. The cationic complexes are isolated as their OTf– salts. These new monometallic species are studied together with the known fac-ReICl(CO)3(qpy) (qpy = 4,4′:2′,2″:4″,4‴-quaterpyridyl) (de Wolf, P.; et al. Inorg. Chim. Acta 2003, 355, 280–285). Coordination of {RuII(NH3)5}2+ centers to the peripheral N atoms of fac-ReICl(CO)3(qpy) and fac-[ReI(CO)3(bcpbpy)(py)]+ affords heterotrimetallic complexes that are isolated as their PF6 – salts. Single-crystal X-ray structures are reported for the solvates fac-ReICl(CO)3(dcbpy)·Me2CO, fac-[ReI(CO)3(dcbpy)(MeCN)]OTf·PhMe, fac-[ReI(CO)3(dcbpy)(py)]OTf·0.5PhMe, fac-[ReI(CO)3(dcbpy)(cpy)]OTf·0.5Me2CO, fac-ReICl(CO)3(bcpbpy)·0.5PhMe, and fac-[ReI(CO)3(bcpbpy)(MeCN)]OTf·MeCN. Cyclic voltammetry reveals irreversible ReII/I processes in all cases, while the trimetallic compounds show a reversible two-electron RuIII/II oxidation wave. Ligand-based reductions are generally irreversible, but reversible waves are observed for the dcbpy complexes. Electronic absorption spectra show strong d → π* metal-to-ligand charge-transfer (MLCT) and intraligand π → π* absorptions. The RuII-based MLCT bands have lower energies and higher intensities than the ReI-based ones. The monometallic species emit weakly in the red/NIR region (λem = 594–732 nm; ϕ = 0.6–8.1%) when excited at 350–520 nm. Molecular first hyperpolarizabilities β for the trimetallic complex salts are measured in MeCN solutions via the hyper-Rayleigh scattering technique at 1064 nm. Stark (electroabsorption) spectroscopic studies on the low-energy MLCT bands in frozen PrCN allow the indirect estimation of static first hyperpolarizabilities β0. The trimetallic complexes have relatively large β0 values, ca. 500 × 10–30 esu or more, which are substantially greater than those of the monometallic species.

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“…Therefore, we address in this work the feasibility of new DSSCs having ruthenium species anchored to the surface of TiO 2 particles by nitrile groups. We have selected for this research the previously described complexes of formulae: [Ru(bpy) 2 (Mebpy-CN)] 2+ (RuL1), [Ru(bpy)(Mebpy-CN) 2 ] 2+ (RuL2), [Ru(Mebpy-CN) 3 ] 2+ (RuL3), and [Re(Mebpy-CN)(CO) 3 Cl] (ReL) (bpy = 2,2′-bipyridine, Mebpy-CN = 4-methyl-2,2′-bipyridine-4′-carbonitrile) [7,8], whose structures are shown in Supplementary Scheme 1. The efficiency of DSSCs sensitized with these complexes have been determined and compared to the standard dye N719 (Ruthenizer 535-bis TBA from Solaronix).…”

mentioning

confidence: 99%

Polypyridyl ruthenium complexes containing anchoring nitrile groups as TiO2 sensitizers for application in solar cells

Ortiz

Longo

Katz

2015

Inorganic Chemistry Communications

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Mono‐ and Dinuclear Complexes of Tricarbonylrhenium(I) with 4‐Methyl‐2,2′‐bipyridine‐4′‐carbonitrile

Cited by 6 publications

References 37 publications

Orientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces

Orientation of Cyano-Substituted Bipyridine Re(I) fac-Tricarbonyl Electrocatalysts Bound to Conducting Au Surfaces

Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores

Polypyridyl ruthenium complexes containing anchoring nitrile groups as TiO2 sensitizers for application in solar cells

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