Ein‐ und zweikernige Kupfer(I)‐ und Silber(I)‐Phosphan‐Komplexe mit β‐Diketonato‐Teilstrukturen

Lang, Heinrich; Leschke, M.; Melter, Michael; Walfort, Bernhard; Köhler, Katrin; Schulz, Stefan E.; Gessner, T.

doi:10.1002/zaac.200300253

Cited by 19 publications

(14 citation statements)

References 62 publications

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“…Moreover, the [L 2 Cu 6 ] core of 3 in the solid state features a cis arrangement of the two tacn units of each ligand strand L – as was also observed for 2 H . The CC stretch of the bound phenylacetylide in 3 was found at 1852 cm –1 , i.e., significantly lower than that in free HCCPh (2119 cm –1 ), − in accordance with the side-on coordination to a Cu(I) ion and substantial π-backbonding. − …”

Section: Resultsmentioning

confidence: 80%

Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate

et al. 2020

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Copper(I) hydride complexes represent a promising entry into formic acid dehydrogenation catalysis. Herein we present the spontaneous decarboxylation of a μ 1,3formate-bridged dicopper(II) complex (1 H ) to a hexacopper(I) hydride cluster (2 H ) upon reduction. Isotopic labeling studies revealed that both the H − and CO 2 originate from the bound μ 1,3 -formate in 1 H , which represents a key step of the metal-mediated formic acid dehydrogenation. The full reaction equation for the conversion of 1 H to 2 H is established. The structure of 2 H features two Cu 3 triangles, each capped by a hydride ligand. Typical hydride reactivity of 2 H is demonstrated by the addition of phenylacetylene, leading to the replacement of the hydrides by alkynide ligands − CCPh (3) while retaining the hexacopper(I) core. Temperature-dependent dynamic behavior in solution on the NMR time scale was observed for both 2 H and 3, reflecting the rich structural landscape of the bis(pyrazolate)-bridged hexacopper(I) core (four isomers each for 2 H and 3) predicted by DFT calculations.

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Section: Resultsmentioning

confidence: 80%

Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate

et al. 2020

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“…Elemental analysis of 19 is in good agreement with the proposed composition. The 31 P{ 1 H} NMR spectrum of 19 is indicative of the coordination of the diphenylphosphanyl group to copper(I) because a typical chemical shift from δ = –18.3 ( 5 ) to –14.9 ppm ( 19 ) is found 26. A broad signal is observed that is attributed to the two isotopes of copper ( 63 Cu, 65 Cu) 27.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reaction Chemistry of Heterodi‐ and Heterotrimetallic Transition‐Metal Complexes Based on 1‐(Diphenylphosphanyl)‐1′‐terpyridylferrocene

et al. 2010

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The reaction of [Fe(η5‐C5H4PPh2)(η5‐C5H4terpy)] (5; terpy = 2,2′:6′,2″‐terpyridin‐4′‐yl) with diverse transition‐metal compounds including [PtCl2(Et2S)2], [Pd(cod)X2], [AuCl(tht)], [CuBr], [Mo(CO)4(nbd)], and [{RhCl(cod)}2] (X = Cl, Br; tht = tetrahydrothiophene; nbd = norbornadiene; cod = cyclooctadiene) to afford heterobi‐ and trimetallic complexes and a coordination polymer is reported. The following compounds were prepared: [Fe(η5‐C5H4PPh2{PtCl2(SEt2)})(η5‐C5H4terpy)] (7), trans‐[PtCl2{(Ph2P‐η5‐C5H4)(η5‐C5H4terpy)Fe}2] (9), [Fe(η5‐C5H4PPh2PdCl2)(η5‐C5H4terpy)] (12), [Fe{η5‐C5H4PPh2(Cl3Pd–)}(η5‐C5H4terpy{(dmso)2ClNi+})] (14), trans‐[PdX2{(Ph2P‐η5‐C5H4)(η5‐C5H4terpy)Fe}2] (16a, X = Cl;16b, X = Br), [Mo(CO)4{(η5‐C5H4PPh2)(η5‐C5H4terpy)Fe}2](17), [Fe{η5‐C5H4Ph2P(CuBr)}(η5‐C5H4terpy)]n (19), [Fe{η5‐C5H4Ph2P(AuCl)}(η5‐C5H4terpy)] (22), [Fe(η5‐C5H4Ph2P{Rh(cod)Cl})(η5‐C5H4terpy)] (23), [Ru({η5‐C5H4Ph2P(AuCl)}(η5‐C5H4terpy)Fe)2]Cl2 (25), and [Fe{η5‐C5H4PPh2(PdCl2)}{η5‐C5H4‐CH=CHC(O)(py)}] (26). The molecular structures of 5, 9, 12, 14, 16b, 22, and 26 in the solid state are reported. They show typical features of related phosphanylferrocenes and terpyridylferrocenes. Characteristic of 12 is a C–H activation as a result of the close distance of palladium to the terpyridyl moiety. Complexes 12, 26, and [PdCl2(dppf)] [dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene], for comparison, were used in preliminary studies as catalysts in the carbon–carbon coupling of iodobenzene with tert‐butyl acrylate to give (E)‐tert‐butyl cinnamate. The conversion amounts to 80 % with a turnover number of 160 and turnover frequency of 48 h–1.

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“…Hence, they attained great interest in, for example, the deposition of metal or metal oxide thin layers by applying diverse deposition techniques, including CVD (=chemical vapor deposition) [ 1 , 11 , 12 , 13 , 14 ], ALD (=atomic layer deposition) [ 15 , 16 , 17 , 18 , 19 ], and spin-coating [ 20 , 21 , 22 ]. In addition, they received great interest in the synthesis of (hetero)multimetallic complexes [ 23 , 24 , 25 , 26 , 27 , 28 , 29 ] as catalysts in organic synthesis [ 30 , 31 , 32 ] and as anticancer drugs (especially copper and rhodium β-diketonates) [ 33 , 34 , 35 ]. Recently, they gained topical attention in the study of electron transfer processes, when, for example, redox-active groups such as ferrocenyls are present, i.e., in zirconium, hafnium, copper(I), copper(II), manganese, ruthenium, rhodium(I), and aluminum β-diketonate complexes [ 36 , 37 , 38 , 39 , 40 , 41 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

Lehrich

Mahrholdt²,

Korb³

et al. 2020

Molecules

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The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η5-C5H4)(η5-C5H5); R = H, 5; nBu, 7; CH2CH2(OCH2CH2)2OMe, 9), [M(κ2O,O′-FcC(O)CHC(O)Fc)n] (M = Ti, n = 3, 10; M = Fe, n = 3, 11; M = BF2, n = 1, 12), and 1-R’-3,5-Fc2-cC3HN2 (R’ = H, 13; Me, 14; Ph, 15) is discussed. The solid-state structures of 5, 7, 9, 12, 13, 15, and 16 ([TiCl2(κ2O,O′-PhC(O)CHC(O)Ph)2]) show that 7 and 9 exist in their β-diketo form. Compound 13 crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule. The electrochemical behavior of 5–7 and 9–16 was studied by cyclic and square-wave voltammetry, showing that the ferrocenyls can separately be oxidized reversibly between −50 and 750 mV (5–7, 9, 12–15: two Fc-related events; 10, 11: six events, being partially superimposed). For complex 10, Ti-centered reversible redox processes appear at −985 (TiII/TiIII) and −520 mV (TiIII/TiIV). Spectro-electrochemical UV-Vis/NIR measurements were carried out on 5, 6, and 12, whereby only 12 showed an IVCT (intervalence charge-transfer) band of considerable strength (νmax = 6250 cm−1, Δν½ = 4725 cm−1, εmax = 240 L·mol−1·cm−1), due to the rigid C3O2B cycle, enlarging the coupling strength between the Fc groups.

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Ein‐ und zweikernige Kupfer(I)‐ und Silber(I)‐Phosphan‐Komplexe mit β‐Diketonato‐Teilstrukturen

Cited by 19 publications

References 62 publications

Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate

Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate

Synthesis and Reaction Chemistry of Heterodi‐ and Heterotrimetallic Transition‐Metal Complexes Based on 1‐(Diphenylphosphanyl)‐1′‐terpyridylferrocene

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

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