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• W2076469504 abstract "Electron-Excess Complexes of Cobalt and Nickel with Cyclobutadiene Ligands: Syntheses, Cyclovoltammetry, and Reactivity[1] A cyclovoltammetric investigation of tetraphenylcyclobutadiene complexes [ML(C4Ph4)]+ [1: ML = NiCp; 2a: ML = Co(C6H6); 2b: ML = Co(mesitylene)] reveals a reversible reduction to paramagnetic complexes 1 and 2a,b with a 19-electron count, and a subsequent irreversible reduction to anions 1- and 2a,b- with a 20-electron shell. Preparative reduction by one equivalent of CpFe(HMB) (HMB = C6Me6) produces the novel 19-electron complexes 1 and 2b. Complex 1 can also be obtained by treatment of 1 · Br with one equivalent of CoCp2 at room temperature while reduction at -20°C with two equivalents of CoCp2 affords a novel C–C-linked adduct CpNi[μ,η3:η4-(C4Ph4–C5H5)]CoCp (5). Above -10°C a slow equilibrium between 5 and its components 1 and CoCp2 is observed with ΔH = 15 kJ/mol for the dissociation process. With an excess of the stronger reductant sodium amalgam the cations 1+ and 2a+ are reduced to give cyclobutenyl complexes ML(η3-1,2,3,endo-4-C4HPh4) [6: ML = NiCp; 7: ML = Co(C6H6)]. 1 reacts with p-nitrobenzyl bromide to give 1 Br and a p-nitrobenzyl addition product CpNi[η3-exo-4-(p-O2NC6H4CH2)-1,2,3,endo-4-C4Ph4] (11) while 2b reacts with MeI to give 2b · I and two isomeric methyl addition products (η5-1,3,5,exo-6-C6H3Me4)Co(C4Ph4)] (12) and (mes)Co(η3-exo-4-Me-1,2,3,endo-4-C4Ph4) (13). Sodium-amalgam reduction of the tetramethylcyclobutadiene cations [(arene)Co(C4Me4)]+ (4a: arene = C6H6; 4b: arene = mesitylene) affords diamagnetic dinuclear compounds of type 8–10 with C–C linkages between C4Me4/C4Me4, arene/C4Me4, and arene/arene rings, respectively." @default.
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• W2076469504 date "1992-07-01" @default.
• W2076469504 modified "2023-10-16" @default.
• W2076469504 title "Elektronenüberschuß‐Komplexe von Cobalt und Nickel mit Cyclobutadien‐Liganden: Synthese, Cyclovoltammetrie und Reaktivität" @default.
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• W2076469504 doi "https://doi.org/10.1002/cber.19921250713" @default.
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