Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

Valle, Eliana Maíra Agostini; Lima, Benedicto Augusto Vieira; Ferreira, Antônio G.; Nascimento, Fábio B. do; Deflon, Victor M.; Diógenes, Izaura C.N.; Abram, Ulrich; Ellena, Javier; Castellano, Eduardo E.; Batista, Alzir A.

doi:10.1016/j.poly.2009.07.029

Cited by 14 publications

(7 citation statements)

References 22 publications

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“…The bond distances and angles listed in Table 2 are in the range expected for ruthenium diphosphine complexes. 7,[12][13][14][29][30][31][32] Similar behavior was observed for the complexes containing 4-methylpyridine and 4-phenylpyridine, as previously reported. 7,29,30 In all three complexes, the dissociated chloride was always the one trans to a phosphorus atom in the precursor cis-[RuCl 2 (P-P) (bipy)], as expected, given the stronger trans effect of the phosphorus atom and in accordance with the X-ray structures.…”

Section: Resultssupporting

confidence: 80%

“…This is confirmed by the X-ray structures of the complexes. 7,29,30 The X-ray structures of [RuCl(4-pic)(P-P)(bipy)]PF 6, [RuCl(Phpy)(P-P)(bipy)]PF 6 and [RuCl(py)(P-P)(bipy)]PF 6 have been published previously. 7,[29][30][31] In this work, we report the structure of [RuCl(4-vnpy)(P-P)(bipy)]PF 6 ( Figure 1).…”

Section: Resultsmentioning

confidence: 99%

“…Thus, in the reactions of the cis-[RuCl 2 (P-P)(N-N)] complexes with N-heterocyclic ligands, the substituted chloride is always the one that is trans to the phosphorus atom, as seen in the X-ray structures of the [RuCl(L)(P-P)(N-N)]PF 6 (L= 4-pic, 4-Phpy, py, 4-vnpy) complexes. 7,29,30 The data in Table 5 show that the Ru d-orbital contributes more effectively to the HOMO of the complexes in the order: MeO-bipy > Me-bipy > H-bipy > Cl-bipy. This is the same order as that of the dissociation rates of the substitution reactions of the cis-[RuCl 2 (P-P)(N-N)] complexes with the N-heterocyclic ligands and also the same order as that of increasing halfwave oxidation potentials of the metal center (Tables 3 and 4).…”

Section: Resultsmentioning

confidence: 99%

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Experimental and theoretical study of the kinetics of dissociation in cis-[RuCl2(P-P)(N-N)] type complexes

Monteiro¹,

Nascimento²,

Valle³

et al. 2010

J. Braz. Chem. Soc.

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-, onde P-P = 1,4-bis(difenilfosfino)butano e N-N = 2,2´-bipiridina, 4,4´-dimetóxi-2,2´-bipiridina, 4,4´-dimetil-2,2´-bipiridina e 4,4´-dicloro-2,2´-bipiridina, L = piridina (py) ou 4-metilpiridina (4-pic), foram estudadas sob condições de pseudo-primeira ordem. As reações ocorrem por um mecanismo dissociativo e as constantes de velocidade nas reações de substituição aumentam com o aumento do pK a dos ligantes N-heterocíclicos e com a diminuição dos potenciais de oxidação do centro metálico. Quanto mais alta é a porcentagem de participação dos orbitais atômicos d do metal na formação do HOMO, conforme calculado pelo método DFT, mais fácil é a dissociação do cloreto da esfera de coordenação do complexo. Nos espectros de 31 P{ 1 H} RMN da série de complexos de fórmula geral [RuCl(L)(P-P)(N-N)]PF 6 , há dois dubletos com Δσ < 1, o que é consistente com produtos formados pela dissociação do cloreto trans ao átomo de fósforo nos precursores.The substitution reactions [RuCl 2 (P-P)(, where P-P = 1,4-bis(diphenylphosphino)butane and N-N = 2,2´-bipyridine, 4,4´-dimethoxy-2,2´-bipyridine, 4,4´-dimethylpyridine-2,2´-bipyridine and 4,4´-dichloro-2,2´-bipyridine, L = pyridine (py) or 4-methylpyridine (4-pic), were studied under pseudo-first order conditions. The reactions proceeded by means of a dissociative mechanism. The rate constants of the substitution reactions increased as the pK a of the N-heterocyclic ligands increased and as the oxidation potential of the metal center decreased. The greater the participation of the atomic d orbitals of the metal in the HOMO, according to DFT calculations, the easier is the dissociation of the chloride from the coordination sphere of the complex. In the 31 P{ 1 H} NMR spectra of the series of complexes of general formula [RuCl(L)(P-P)(N-N)]PF 6 , there are two doublets with Δσ < 1. This is consistent with products formed by dissociation of the chloride trans to one of the phosphorus atoms in the precursors.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Experimental and theoretical study of the kinetics of dissociation in cis-[RuCl2(P-P)(N-N)] type complexes

Monteiro¹,

Nascimento²,

Valle³

et al. 2010

J. Braz. Chem. Soc.

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“…Calc. for C 46 TBAP, scan rate 100 mV s À1 , at room temperature, with E ox = 1200 mV and E 1/2 = 1125 mV, close to those found for similar chlorine complexes containing dppb, diimines and N-heterocyclic as ligands [20,21,32,[34][35][36][37][38].…”

Section: Synthesis Of [Rucl(dppb)(55 0 -Me-bipy)(4-vpy)](pf 6 ) (3)supporting

confidence: 80%

Modified glassy carbon electrode with AuNPs using cis-[RuCl(dppb)(bipy)(4-vpy)]+ as crossed linking agent

et al. 2014

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“…In this case only the complex SCAR06 presents chloride coordinated to the ruthenium, but it was showed that only one trans to the phosphorus atom is dissociated from the metal [37,38].…”

Section: In Vitro Structureeactivityerelationship (Sar)mentioning

confidence: 95%

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

Pavan

Poelhsitz

Barbosa

et al. 2011

European Journal of Medicinal Chemistry

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Driving forces in substitution reactions of octahedral complexes: The influence of the competitive effect

Cited by 14 publications

References 22 publications

Experimental and theoretical study of the kinetics of dissociation in cis-[RuCl2(P-P)(N-N)] type complexes

Experimental and theoretical study of the kinetics of dissociation in cis-[RuCl2(P-P)(N-N)] type complexes

Modified glassy carbon electrode with AuNPs using cis-[RuCl(dppb)(bipy)(4-vpy)]+ as crossed linking agent

Ruthenium(II) phosphine/diimine/picolinate complexes: Inorganic compounds as agents against tuberculosis

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