Highly selective telomerization reactions of a number of short-chain glycol nucleophiles with 1,3-butadiene have been achieved in aqueous biphasic systems employing the water-soluble catalyst system Pd(acac) 2 /TPPTS. For all substrates the selectivity for the obtained monotelomers 5 ± 7 reached ! 95% whereas butadiene dimers 3, octadienols 4 and ditelomers like 2 were produced only in trace amounts. The order of reactivity is ethylene glycol >> 1,3-propylene glycol % glycerol > 1,4-butylene glycol, which is in agreement with generally observed trends. The scope and limitations of these reactions are discussed in terms of obtained yields and achievable catalyst productivities (total turnover numbers).

The synthesis of valuable ethers, carboxylic acids and alcohols has been achieved by telomerization and hydrogenation procedures using only butadiene, carbon dioxide, ethylene glycol and hydrogen as starting materials. High product selectivities and yields have been realized in all reaction steps and catalyst recycling has been achieved by liquid-liquid-two-phase techniques. This way, ecologically and economically favorable chemical syntheses have been demonstrated using the waste gas carbon dioxide and other cheap feedstocks. † This work was presented at the Green Solvents for Catalysis Meeting held in Bruchsal, Germany 13-16th October 2002.

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Reactions involving Fe(NO)2(CO)2 and the bis(phosphine) ligands bis(diphenylphosphino)methane (DPPM), bis(diphenylphosphino)acetylene (DPPA), 1,6-bis(diphenylphosphino)hexane (DPPH), and 1,4-bis(diphenyl phosphino)benzene (DPPB) have been examined. From these reactions, the mononuclear complex, Fe(κ1-DPPM)(NO)2(CO) 3, linear dinuclear species of the type Fe2(µ-L)(NO)4(CO)2 (L = Ph2PCH2PPh2 4, Ph2PC[Formula: see text]CPPh2 5, Ph2PCH2(CH3)4CH2PPh2 6, and Ph2P(p-C6H4)PPh2 7), and macrocyclic dinuclear species of the type Fe2(µ-L)2(NO)4 (L = Ph2PCH2PPh2 8 and Ph2PC[Formula: see text]CPPh2 9) were isolated and spectroscopically characterized. For 4, 5, 8, and 9, the solid-state molecular structures of the products were determined by use of single-crystal X-ray diffraction techniques. Key words: dinitrosyliron, iron nitrosyls, dinuclear macrocycles, bis(phosphine) complexes.