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The synthesis of diethylindiumdiphenylphosphinate and the crystal structures of dimethylgalliumdiphenylphosphinate and diethylindiumdiphenylphosphinate are reported. The two structures confirm the proposed dimeric nature of the title compounds with bridging diphenylphosphinate groups. [Ph2P(O)2Ga(CH3)]2 crystallizes triclinically, PĪ, with a = 9.483(6), b = 10.216(4), c = 8.780(9)Å, α = 101.66(5)°, β = 113.74(5)°, γ = 69.93(5)° and Ζ = 1 (dimer). [Ph2P(O)2In(C2H5)2]2 crystallizes monoclinically, C2/c, with a = 19.971(5), b = 8.590(2), c = 19.457(5)Å, β = 102.91(2)° and Ζ = 4 (dimers). Both structures contain tetrahedrally coordinated phosphorous and metal atoms.

The electrochemical synthesis of iron, cobalt, and nickel carbonyl compounds from metal acetylacetonates of oxidation state + II or + III and from metal anodes is described, solvent effects and the problem of cluster formation are discussed.

A theoretical model for the electrochemical synthesis of transition metal complexes in low oxidation states has been developed on the basis of Pearson’s HSAB concept. A MO description is used to discuss the important practical implications of the model.

Following known procedures for the preparation of nickel complexes as precursors to active contact species for the cyclooligomerization of acetylene we report the electrochemical formation of Ni(CO)2(PPh3)2 and its use in a one-pot trimerization of acetylene to benzene. Further investigations demonstrate the possibility to simultaneously produce and use as catalysts active nickel solvates generated from nickel anodes for the cyclization of acetylene to benzene and/or cyclooctatetraene.

The electrochemical synthesis of iron, cobalt, and nickel carbonyl derivatives with phosphane ligands from metal anodes is described.