BIS(α,β‐DIONEDIOXIMATO)METAL COMPLEXES: SOLID‐STATE DESIGN BY MOLECULAR ENGINEERING*

Endres, H.; Keller, Heimo J.; Lehmann, R.; Sand, Henrik; Vu, Dong; Poveda, Arnulfo

doi:10.1111/j.1749-6632.1978.tb39450.x

Cited by 5 publications

(3 citation statements)

References 43 publications

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“…The 'H NMR spectrum for the trans-RJ isomer should give rise to two methyl doublets of the equal intensities, since the axial methyl group should exhibit, in principle, a different chemical shift from that of the equatorial methyl group. 16 The CD curve of Ib is fairly different from and apparently less intense than that of Ia (trans-S,S isomer (Figure 3)). For the trans-RJ isomer, the conformational effects will not contribute to the CD, because the five-membered rings has the opposite conformation.…”

Section: Resultsmentioning

confidence: 90%

“…The vicinal effects from Cmethyl groups would be relatively small on the CD of trans-[CoC12N4]+ type complexes as discussed previously. 16 The CD curve of lb is fairly different from and apparently less intense than that of la (trans-5,5 isomer (Figure 3)).…”

Section: Resultsmentioning

confidence: 92%

“…One of the complexes having Q symmetry (lib) was isolated and purified by repeated recrystallizations. cm"1 (log e) cm'1 Oler) 16.00 (1.71) 15.24 (-0.54) 16.95 (+0.41) 22.1 (1.4) 21.69 (-0.75) 25.77 (1.7) 25.64 (+0.34) 16.00 (1.72) 16.26 (+0.17 15.20 (+0.98) 20.62 (1.56) 20.49 (-1.59) 24.57 (1.82) 25.64 (+0.25) 15.58 (1.73) 15.70 (-0.33) 20.83 (1.69) 20.41 (+0.80) 24.75 (1.99) 25.97 (-0.19) 15.50 (1.60) 14.49 (-0.42) 16.26 (+0.69) 21.60 (1.48) 20.49 (-0.61) 24.45 (1.87) 24.39 (+0.19) 19.42 (2.20) 18.35 (+2.47) 20.49 (-1.51) 27.78 (2.12) 25.51 (+2.47) 28.57 (+0.41) 18.87 (2.24) 18.05 (+2.19) 20.37 (-0.46) 26.88 (2.17) 25.13 (+0.55) 28.01 (+0.42) whatever isomers of dichloro complexes used as the starting material. plexes are given in Figures 6 and 7.…”

Section: Resultsmentioning

confidence: 99%

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Isomers of cobalt(III) complexes containing quadridentate ligands with a six-membered chelate ring. Optically active 2,3,2-tet derivatives

Ajioka¹,

Yano²,

Saburi³

et al. 1981

Inorg. Chem.

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RCSO)] and that [Pt0(PPh3)2[(Z)-(MeS)RCSO]] likewise gave rise to cis-(E)-[Pt"(MeS)(PPh,),(RCSO)] illustrate that during the oxidative-addition reaction isomerization of the sulfine skeleton occurs. Three types of isomerization pathway are possible: First, there could be an equilibrium between the pseudoallylic intermediates, analogous to the syn-anti interchange found in the complexes [P~CI(PR,)(V~-H,CC(H)CH~)].~~ Second, a direct equilibrium between the two oxidativeaddition stereoisomers &-(E)-and cis-(Z)-[Pt"(MeS)-(PPh,),(RCSO)] can be envisaged, perhaps catalyzed by trace impurities. Isomerization under influence of base has been observed for free sulfines.40A third possibility could be a process involving an impurity-catalyzed isomerization of free sulfine (generated by a dissociative process of the coordination compounds) followed by recoordination of the sulfine.In order to gain more insight into the isomerization of oxidative-addition stereoisomers, we have studied the isomerization of cis-( E )and cis-(Z) -[ Pt "C1( PPh,) 2( RSCSO)] (R = p-MeC6H4, Ph), oxidative-addition products of the sulfine (E)-(RS)ClCSO. The lability of the C-C1 bond with respect toward oxidative addition to PtO should prohibit both a reductive coupling reaction of C1 and RSC=S=O and the existence of pseudoallylic intermediates. The results will be described in a forthcoming paper.34 In order to investigate (39) Vrieze, K. "Dynamic Nuclear Magnetic Resonance Spectroscopy"; Jackman, L. M., Cotton, F. A., Eds.; Academic Press: New York, 1975; (40) Bonini, B. F.; Maccagnani, G . J. Chem. SOC., Perkin Tram. 2 1978, pp 441-487. 121 8-1 224.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 92%