Pentamethylcyclopentadienyl rhodium(III) trifluorovinyl phosphine complexes and attempted intramolecular dehydrofluorinative coupling of pentamethylcyclopentadienyl and trifluorovinyl phosphine ligands

Synthesis and characterization of half-sandwich Rh, Ir complexes containing mono-thiolate-ortho-carborane ligand

“…5. The solid state molecular structure reveals the geometry at the Ir(III) center are analogous to these of (16) Å, are all comparable to those reported for the Ir(III) complexes with P,S-ligands [49,50].…”

“…The Ir (III) center is also a three-legged piano-stool with Ir atom coordinated by the h 5 -Cp * , one Carb S ligand, one phosphorus atom and one chloride atom. The distances Rh(1)eS(1) 2.3848(9) Å, Rh(1)eP (1) 2.3157(10) Å are a litter shorter than that of Rh(1)eCl(1) 2.4122 (9) Å, which are all within the range of known values for them in analogous complexes [10,31,49]. And the lengths Ir(1)eP(1) 2.2998 (13) Å, Ir(1)eS(1) 2.3821(12) Å and Ir(1)eCl(1) 2.4088(12) Å, are all comparable to those reported for the Ir(III) complexes with P,Sligands [48].…”

Fluoroalkenyl, fluoroalkynyl and fluoroalkyl phosphines

“…1528 for PEt 2 (CF5 5CF 2 ) to 1698 for PCy 2 (CF5 5CF 2 ). Interestingly the cone angle for PhP(CF5 5CF 2 ) 2 (1618) appears to be somewhat smaller than that of PhP(C 6 F 5 ) 2 (1718) and this is suggested as the reason why PhP(CF5 5CF 2 ) 2 will form a complex with [Cp*RhCl(m-Cl)] 2 but that PhP(C 6 F 5 ) 2 does not [40]. It was also shown that intramolecular dehydrofluorinative coupling of rhodium bound pentafluoromethylcyclopentadienyl and perfluorovinyl phosphine ligands can occur.…”

“…Comparison of the carbonyl stretching frequencies obtained from the rhodium complexes demonstrate that they are poorer donors than nonfluorinated phosphines, e.g. for the complex of PhP(CF5 5CF 2 ) 2 n(CO) = 2002 cm À1 which compares with 1979 cm À1 for PPh 3 , 1996 cm À1 for PhP(C 6 F 5 ) 2 [40], and 2014 cm À1 for P(OMe) 3 , Table 1. Thus, whilst the perfluorovinyl group appears to have a smaller steric demand than -C 6 F 5 , it appears to possess a comparable electron-withdrawing effect, and this is reflected in the x values for these groups both of which are ca.…”

Intramolecular dehydrofluorinative coupling of η6-arene and fluoroarylphosphine ligands in ruthenium complexes

“…The coupling reaction was assessed by in situ NMR experiments on a range of cationic complexes containing different arene and phosphine ligands and on a neutral complex. This strategy has proved useful for assessing the analogous reaction with h 5 -cyclopentadienide rhodium complexes of polyfluoroaryl- [2] and trifluorovinyl-phopshines [25].…”