Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(&lt;FONT FACE=Symbol&gt;s,s&lt;/FONT&gt;)-1,3-butadiyne-1,4-diyl ligand

Stein, Edison; Oki, Sergio Y.; Vichi, Eduardo J. S.

doi:10.1590/s0103-50532000000300009

Cited by 6 publications

(1 citation statement)

References 7 publications

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“…The stronger absorption at ca. 1980 cm −1 is not readily assigned, with the energy appropriate for ruthenium hydride, 61,62 acetylide, 63 allenylidene, 64,65 or carbonyl 53 complexes, none of which were detected by additional spectroscopic techniques.…”

Section: ■ Introductionmentioning

confidence: 93%

Coordinating Tectons 4: Coordination Chemistry of the 4,5-Diazafluoren-9-yl Moiety as a Metallo-Ligand for Allenylidene Complexes

2015

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We describe how the 4,5-diazafluoren-9-yl moiety has been utilized in the construction of multinuclear complexes incorporating a ruthenium(II) allenylidene functionality. The coordination chemistry of diazafluorenylterminated allenylidene complexes is limited by the sensitivity (instability) of the allenylidene moiety under a variety of synthetic conditions. In contrast the κ 2 -N,N′-coordination of the diazafluorenyl propargylic alcohol (alkynol) to a metal center prior to allenylidene formation provides a facile route toward the synthesis of multinuclear allenylidene coordination complexes. Our synthetic attempts and successes are discussed in combination with spectroscopic and electronic characterization of the latter cases. ■ INTRODUCTIONThere exists a fundamental interest in the properties of multimetallic molecular complexes, to afford both understanding and applications in catalysis, 1−3 molecular electronics, 4−6 photochemistry, 7,8 and combinations thereof. 9−12 Of particular interest are those complexes in which the metal sites cooperate to yield synergistic properties largely absent in mononuclear analogues. To this end, molecules in which multiple metal sites are connected by conjugated organic bridges are of particular interest, as such bridging moieties are expected to foster increased degrees of interaction between the metal sites. The synergistic effects of the metal sites may then be readily tuned via synthetic modifications to the bridging moiety or to the coordination sphere of the pendant metal sites or by changing the identity of the metal atom(s). 13 The prevalent examples of such complexes are those bearing symmetrical (oligo)ethynylene 14,15 or polypyridyl bridging ligands. 16,17 It is our goal to synthesize discrete molecular components that can be assembled into multinuclear complexes via a coordination chemistry methodology, i.e., coordinating tectons. 18−20 Specifically we seek also to develop these tectons as asymmetric components in order to provide facile synthetic access to heterometallic complexes, and thus more readily elucidate and tune the effects of a particular metal site on the molecular properties of the complex as a whole. Our lab and others have reported on transition metal σ-alkynyl complexes derived from 5-ethynyl-2,2′-bipyridine and the successful κ 2 -N,N′-complexation of additional d-and f-block metals to the pendant diimine moiety. 19,21−28 We have previously reported the synthesis and characterization of the complexes [MCl(PP) 2 (CC{4,5-diazafluoren-9-yl})]PF 6 (M = Ru, Os; PP = dmpe, dppm, dppe; not all combinations), 18 and in this investigation we describe efforts to synthesize multinuclear complexes incorporating 1, Scheme 1. Recent developments in metallocumulene chemistry have been reported. 29 Contemporary with our investigations examples of the formation of bimetallic complexes by reaction of metal precursors with the closely related allenylidene

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Section: ■ Introductionmentioning

confidence: 93%

Coordinating Tectons 4: Coordination Chemistry of the 4,5-Diazafluoren-9-yl Moiety as a Metallo-Ligand for Allenylidene Complexes

2015

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Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

et al. 2018

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The syntheses of oligo(p‐phenylene ethynylene)s (OPEs) end‐functionalized by a nitro acceptor group and with a ligated ruthenium unit at varying locations in the OPE chain, namely, trans‐[Ru{(C≡C‐1,4‐C6H4)nNO2}(C≡CR)(dppe)2] (dppe=1,2‐bis(diphenylphosphino)ethane; n=1, R=1,4‐C6H4C≡C‐1,4‐C6H4C≡CPh, 1,4‐C6H4NEt2; n=2, R=Ph, 1,4‐C6H4C≡CPh, 1,4‐C6H4C≡C‐1,4‐C6H4C≡CPh, 1,4‐C6H4NO2, 1,4‐C6H4NEt2; n=3, R=Ph, 1,4‐C6H4C≡CPh), are reported. Their electrochemical properties were assessed by cyclic voltammetry, their linear optical properties and quadratic and cubic nonlinear optical properties were assayed by UV/Vis/NIR spectroscopy, hyper‐Rayleigh scattering studies employing nanosecond pulses at 1064 nm, and broad spectral range Z‐scan studies employing femtosecond pulses, respectively, and their linear optical properties and vibrational spectroscopic behavior in the formally RuIII state was examined by UV/Vis/NIR and IR spectroelectrochemistry, respectively. The potentials of the metal‐localized oxidation processes are sensitive to alkynyl‐ligand modification, but this effect is attenuated on π‐bridge lengthening. Computational studies employing time‐dependent density functional theory were undertaken on model complexes, with a 2D scan revealing a soft potential‐energy surface for intra‐alkynyl‐ligand aryl‐ring rotation; this is consistent with the experimentally observed blueshift in optical absorption maxima. Quadratic optical nonlinearities are significant and cubic NLO coefficients for these small complexes are small. The optimum length of the alkynyl ligands and the ideal metal location in the OPE to maximize the key coefficients have been defined.

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Synthesis, structural analysis, redox properties and in vitro antitumor evaluation of half-sandwich complexes of Ru(II) with aminocoumarins

et al. 2017

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Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(<FONT FACE=Symbol>s,s</FONT>)-1,3-butadiyne-1,4-diyl ligand

Cited by 6 publications

References 7 publications

Coordinating Tectons 4: Coordination Chemistry of the 4,5-Diazafluoren-9-yl Moiety as a Metallo-Ligand for Allenylidene Complexes

Coordinating Tectons 4: Coordination Chemistry of the 4,5-Diazafluoren-9-yl Moiety as a Metallo-Ligand for Allenylidene Complexes

Linear Optical, Quadratic and Cubic Nonlinear Optical, Electrochemical, and Theoretical Studies of “Rigid‐Rod” Bis‐Alkynyl Ruthenium Complexes

Synthesis, structural analysis, redox properties and in vitro antitumor evaluation of half-sandwich complexes of Ru(II) with aminocoumarins

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