Reaction of the dicobalt alkyne compound Co2(CO)6(μ-dmad) with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Spectroscopic properties, X-ray diffraction data, and thermal ... View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2004-08

AUTHORS

Chun-Gu Xia, Simon G. Bott, Michael G. Richmond

ABSTRACT

Treatment of Co2(CO)6(μ-dmad) (where dmad = dimethyl acetylenedicarboxylate) with the bidentate ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in the presence of added Me3NO affords the new alkyne compound Co2(CO)4(bpcd)(μ-dmad) in good yield. Both IR and 31P NMR spectroscopies indicate that the bpcd ligand is coordinated to a single cobalt center in a chelating fashion in solution. The solid-state structure of Co2(CO)4(bpcd)(μ-dmad) is identical to the solution structure Co2(CO)4(bpcd)(μ-dmad), as determined by X-ray diffraction analysis. Co2(CO)4(bpcd)(μ-dmad) crystallizes in the triclinic space group P-1, a = 10.7460(8) Å, b = 11.628(2) Å, c = 15.077(1) Å, α = 95.831(9)°, β = 91.205(7)°, γ = 101.526(9)°, V = 1834.7(3) Å3, Z = 2, and dcalc = 1.514 g/cm3; R = 0.0489, Rw = 0.0528 for 2854 reflections with I > 3σ(I). The thermal reactivity of Co2(CO)4(bpcd)(μ-dmad) has been briefly explored by spectroscopic methods, and evidence is presented for the attack of one of the PPh2 groups on an alkyne carbon atom in Co2(CO)4(bpcd)(μ-dmad) to from the zwitterionic hydrocarbyl compound Co2(CO)4(μ-η2:η2:η1:η1-(MeO2C)=C(CO2Me)PPh2C=C(PPh2)C(O)CH2C(O)] upon thermolysis. The redox chemistry of both Co2(CO)4(bpcd)(μ-dmad) and Co2(CO)4[μ-η2:η2:η1:η1-(MeO2C) C=C(CO2Me)PPh2C=C(PPh2)C(O)CH2C(O)] has been explored by cyclic voltammetery. More... »

PAGES

513-521

Identifiers

URI

http://scigraph.springernature.com/pub.10.1023/b:jocc.0000042019.54785.9a

DOI

http://dx.doi.org/10.1023/b:jocc.0000042019.54785.9a

DIMENSIONS

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