Synthesis and structural characterization of new mixed-ring indenyl derivatives of molybdenum containing phosphorus ligands

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

“…This was further confirmed by reacting CpFe(CO) 2 I with a mixture of both PPh 3 and P(OMe) 3 Thus a solvent-free reaction does not always benefit from increased localised concentration (and contact) effects between reactants. Therefore, other factors have to be considered when interpreting these reactions.…”

“…Thus, even though the phosphites used in this study are liquids and hence should have a better ability to 'mix' with solid reactants as compared to corresponding solid phosphines, generally the solvent-free substitution reaction of the phosphines are much faster than those of the corresponding phosphites. Table 1 Solventless reactions between C 5 H 5 Fe(CO) 2 I and P(OR) 3 to yield C 5 H 5 Fe(CO)P(OR) 3 The solid-liquid study has further demonstrated the impact of solventless reactions in organometallic chemistry.…”

“…The reactions of metal complexes with phosphite ligands (many of which exist as liquids at room temperature) have been widely reported in a range of solvents [3][4][5][6]. For example, trialkylphosphite ligands P(OR) 3 (R = CH 3 , C 2 H 5 ) have been shown to react with R 0 CpM(CO) 2 X complexes in benzene and toluene as solvents to produce the compounds R 0 CpM(CO)[P(OR) 3 ]X (where R 0 = H, Me, COOMe, etc.…”

“…The products were isolated and fully characterised (see Supplementary materials for details). As can be seen from Table 1, both the catalyzed and uncatalyzed reactions led only to the formation of neutral products CpFe(CO)[P(OR) 3 …”

“…This would suggest that reactions performed between a solid and a liquid reactant would also occur more rapidly than when performed in a solvent provided again that the solid reactant melted/dissolved under the reaction conditions used. These reagents would also provide a single liquid phase for the reaction.To explore this possibility we have investigated the reaction between liquid phosphite reagents, P(OR 0 ) 3 , and solid RCpM(CO) 2 I reactants to give RCpM(Co)[P(OR 0 ) 3 ]I (M = Fe, Ru; R = H, Me and R 0 = CH 3 , C 2 H 5 , C 6 H 5 ) (Scheme 1).The reactions of metal complexes with phosphite ligands (many of which exist as liquids at room temperature) have been widely reported in a range of solvents [3][4][5][6]. For example, trialkylphosphite ligands P(OR) 3 (R = CH 3 , C 2 H 5 ) have been shown to react with R 0 CpM(CO) 2 X complexes in benzene and toluene as solvents to produce the compounds R 0 CpM(CO)[P(OR) 3 ]X (where R 0 = H, Me, COOMe, etc.…”