Platinum group metal complexes of arylphosphine ligands containing perfluoroalkyl ponytails; crystal structures of [RhCl2(η5-C5Me5){P(C6H4C6F13-4)3}] and cis- and trans-[PtCl2{P(C6H4C6F13-4)3}2]

Synthesis and coordination chemistry of perfluoroalkylated dithiophosphate ligands

“…We have been particularly interested in the electronic and steric implications of the perfluoroalkyl substituents on the donor properties of perfluoroalkylated ligands in coordination chemistry and the structural impact of the fluorous ponytails on the solidstate structures of the coordination compounds [5][6][7][8][9]. Although the coordination chemistry of perfluoroalkylated P-, N-and O-donor ligands has been extensively evaluated [4], there have been no recent examples of complexes incorporating S-donor ligands.…”

Hydrocarboxylation of Terminal Alkenes in Supercritical Carbon Dioxide

“…65:35, which is close to the catalytic results (Entry 2, Table 2). In the 13 C NMR spectra the signal corresponding to free CO can be observed at δ = 182 ppm and a small signal at δ = 181 ppm could indicate the presence of species with coordinated CO, which could not be differentiated in the 31 [21] together with the signal of the free phosphane. After the acid addition no significant changes were observed and no acid formation was detected in the 13 C{ 1 H} NMR spectrum.…”

Fluorous Organometallic Chemistry

“…These have generated fluorous analogues of almost every class of organometallic complex that have, almost without fail, been thoroughly characterised analytically and spectroscopically, generating a large amount of new insight into fluorous systems. Studies on the single most extensively studied class of organometallic complex, the Vaska's analogues, have been used to establish the electronic influence of incorporating the fluorinated substituents, but, perhaps, the insight into the role of the fluorous solvent and/or substituents on the kinetics and mechanism of oxidative addition in these systems, mentioned in the work from two groups [47,50], has been overlooked. Structurally, more than 20 single crystal structure determinations have been reported on fluorous organometallic complexes, and these reveal two significant facts: The perfluoroalkyl groups have little or no impact upon the key structural features in the first metal coordination sphere (M-L bond lengths, L-M-L 0 bond angles), but they dominate the packing in the solid-state generating fluorous and non-fluorous domains throughout the extended structures.…”

“…A number of these systems have been the subject of single crystal X-ray analyses, which generally revealed that the ponytails had little influence on the structural features of the metal centres (bond lengths, bond angles) but dictated the packing of these species in the solid state. Oxidative addition reactions (of H 2 , O 2 , MeI, C 8 F 17 C 2 H 4 I) on the iridium Vaska's complex analogues {P(C 2 H 4 C 6 F 13 ) 3 and PPh n (C 6 H 4 -4-C 6 F 13 ) 3Àn (n ¼ 0, 1, 2) ligands} generate the anticipated octahedral Ir(III) species, but in-depth studies suggest a different mechanism for the addition reactions to these fluorousfunctionalised complexes compared to those with protio ligands [46,47,50]. The hydroformylation catalyst [HRh(CO){P(C 2 H 4 C 6 F 13 ) 3 } 3 ] is formed quantitatively in the reaction of the phosphine with [Rh(CO) 2 (acac)] under Syngas in a closed system [62].…”

“…Cleavage [50,52,[55][56][57]61] that have been used to establish the impact of the fluorous substituents on the electronic, physical and structural properties of the metal complexes. A number of these systems have been the subject of single crystal X-ray analyses, which generally revealed that the ponytails had little influence on the structural features of the metal centres (bond lengths, bond angles) but dictated the packing of these species in the solid state.…”