Organometallic chemistry in the melt phase

Solvent-Free Synthesis of Luminescent Copper(I) Coordination Polymers with Thiourea Derivatives

“…This can be classified as a green chemistry approach, whose guidelines have been provided, although some controversy still abounds. 12 In this context, mechanochemistry has proven to be a groundbreaking approach, particularly useful in the preparation of new materials. It combines a high success rate with low-cost, environmentally friendly procedures, products that may differ from those obtained via solution reactions, easy workup, short reaction time, and high yields.…”

Substitution reactions of Fe and Ru complexes with liquid phosphite ligands in the absence of solvents

“…In contrast, in refluxing benzene, the catalyzed reaction between MeCpFe(CO) 2 I with P(OMe) 3 easily afforded the product MeCpFe(CO)[P(OMe) 3 ]I [17]. Similar solvent-free (melt) studies with solid phosphines were observed to be accelerated when an electron donating substituent is attached to the Cp ligand, although the product obtained was the salt product, [MeCpFe(CO) 2 [P(OR) 3 ]I [12].…”

“…Extensive studies of many so-called 'solid-solid' (solventless) reactions in organic [1] and organometallic [2] chemistry have shown that the reactions occur in the melt phase. In the melt studies between solid reagents that have been reported to date the general consensus is that solvent-free (solventless) reactions occur more rapidly than reactions performed in solvents due to enhanced concentration effects.…”

Chapter 7. Ball-milling Mechanochemical Synthesis of Coordination Bonds: Discrete Units, Polymers and Porous Materials

“…25 The Coville group has conducted extensive studies of solvent-free ligand exchange reactions on organometallic complexes 12 and, in some cases, established that the reactions are mediated by a low melting eutectic phase (Figure 7.5b). 63,64 The first reported mechanosynthesis of a coordination polymer by design appears to have been based on a ligand exchange reaction involving the binuclear copper(II) acetate paddlewheel cluster: manual grinding of copper(II) acetate monohydrate with 1,3-bis(4-pyridyl)propane (pn) produced the water inclusion compound of a 1D polymer by mechanochemical replacement of copper-coordinated water molecules with bridging pn ligands (Figure 7.5c).…”

“…Pioneering reports on the synthesis of coordination polymers date from early 2000s, 1 and mechanochemical synthesis of discrete metal-organic complexes, although noted in 1970s, 7 have remained largely unexplored until the twenty-first century. Despite a late beginning, the area of metal-organic mechanochemistry has developed with explosive velocity and now encompasses a vast diversity of materials, from molecular cages 8 and squares, microporous metalorganic frameworks (MOFs), 9 luminescent coordination polymers 10 and organic light-emitting diode (OLED) materials 11 to organometallics, 12 pharmaceutical derivatives 13 and metallodrugs. 14 Notably, the first techniques 15 for in situ monitoring of the mechanisms of mechanochemical reactions using X-ray powder diffraction and Raman spectroscopy 16 have focused largely on the assembly of coordination polymers and MOFs by milling.…”