1995
DOI: 10.1021/ic00128a016
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Effect of Conformational Constraints on Gated Electron-Transfer Kinetics. A Multifaceted Study on Copper(II/I) Complexes with cis- and trans-Cyclohexanediyl-[14]aneS4

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Cited by 42 publications
(82 citation statements)
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“…The copper boron distance is with 2.065(2) Å very similar to the one in [Cu­{B­(Pn tBu ) 3 }­Cl] (2.068(3) Å) but significantly shorter than in triphosphine boratranes. , The S–Cu–B–N torsion angles are in the range of 35.18(13)°–38.47(13)° aligning the heterocycles in a paddlewheel-like twisted fashion around the copper. The copper chlorine bond distance is with 2.2871(6) Å in the typical range for similar complexes. , On the one hand, the crystal structure reveals the methyl groups pointing away from the chlorine atom, so larger substituents would be necessary for a significant steric impact at the metal center. On the other hand, the methyl group shields the sulfur atom to avoid its reaction with electrophiles, which is known for related methimazolyl borate systems …”
Section: Resultsmentioning
confidence: 99%
“…The copper boron distance is with 2.065(2) Å very similar to the one in [Cu­{B­(Pn tBu ) 3 }­Cl] (2.068(3) Å) but significantly shorter than in triphosphine boratranes. , The S–Cu–B–N torsion angles are in the range of 35.18(13)°–38.47(13)° aligning the heterocycles in a paddlewheel-like twisted fashion around the copper. The copper chlorine bond distance is with 2.2871(6) Å in the typical range for similar complexes. , On the one hand, the crystal structure reveals the methyl groups pointing away from the chlorine atom, so larger substituents would be necessary for a significant steric impact at the metal center. On the other hand, the methyl group shields the sulfur atom to avoid its reaction with electrophiles, which is known for related methimazolyl borate systems …”
Section: Resultsmentioning
confidence: 99%
“…These are reflected in the individual rate and equilibrium parameters for these systems as generated from the matching of computer simulations to a huge array of experimental CVs as shown in Table 8. Extensive cross-reaction kinetic studies were also made on these Cu(II/I) systems 136,137 from which it became possible to calculate the selfexchange rate constants for each of the two pathways in Scheme 1, k 11(A) and k 11(B) ( Table 8). The combination of these latter values with the equilibrium constants for the conformational changes, K OQ (i.e., k OQ /k QO ) and K RP (i.e., k RP /k PR ), as determined from the CV measurements, 51 has permitted an estimation of the specific self-exchange rate constants repre- [14]aneS4; L2 ) cis-cyhx- [14]aneS4; L3 ) trans-cyhx- [14]aneS4; L7 ) syn-cis,cis-dicyhx- [14]aneS4; L8 ) anti-cis,cisdicyhx- [14]aneS4; L9 ) meso-trans,trans-dicyhx- [14]aneS4; L10 ) dl-trans,trans-dicyhx- [14]aneS4; L11 ) cis,trans-dicyhx- [14]aneS4 (see Figure 10) sentative of the two stable oxidation states exchanging electrons directly with their metastable counterparts: 137 These latter values are included in Table 8.…”
Section: Thiaether Complexesmentioning
confidence: 99%
“…Rorabacher recently reviewed ET reactions by Cu(II)/(I) centers, 13 in which he seems to have confirmed that the gated ET reactions exhibited by copper complexes are successfully explained by this scheme. 8- 12 In general, ET reactions of Cu(II)/(I)-polythioether complexes proceed through path A in Scheme 1, and the direction in which the estimated self-exchange rate constant is much smaller than that directly measured by NMR is gated: i.e. the selfexchange rate constant estimated from the non-gated direction is almost identical to that measured directly by the NMR method.…”
Section: Introductionmentioning
confidence: 98%
“…Among investigations carried out to date, intensive and systematic studies by Rorabacher and co-workers seem to have largely improved understandings of the gated phenomena: they examined ET reactions of Cu(II)/(I)-macrocyclic polythioether complexes and found that the coordination structural change takes place essentially at the Cu(I) site while the coordination geometry around the Cu(II) species is not largely altered. [8][9][10][11][12] They related this phenomenon to the biologically important catalytic processes and postulated a dual-pathway Square Scheme described in Scheme 1. Rorabacher recently reviewed ET reactions by Cu(II)/(I) centers, 13 in which he seems to have confirmed that the gated ET reactions exhibited by copper complexes are successfully explained by this scheme.…”
Section: Introductionmentioning
confidence: 99%