Synthesis of [Ni(η2-CH2C6H4R-4){PPh(CH2CH2PPh2)2}]+ (R=H, Me or MeO) and protonation reactions with HCl

Mechanistic Information from Low-Temperature Rapid-Scan and NMR Measurements on the Protonation and Subsequent Reductive Elimination Reaction of a (Diimine)platinum(II) Dimethyl Complex

“…There is a definite possibility that rapid proton transfer may occur, inter-or intramolecularly, between these sites, and this makes it far from trivial to assess which is the kinetically preferred site of protonation. [34][35][36][37][38] It is commonly considered that proton transfers at carbon sites or at metal centers are intrinsically slow because of the considerable geometric and electronic rearrangements that arise as a consequence of the protonation event and that protonation of a hydrido ligand may be kinetically preferred because the accompanying structural/ electronic changes are less significant. [39][40][41] The protonation process described herein appears to be rather fast for a welldocumented 15 metal-centered process and is characterized by a low activation enthalpy.…”

“…Protonation can occur at multiple sites in such complexes, either at the metal or at a ligand. There is a definite possibility that rapid proton transfer may occur, inter- or intramolecularly, between these sites, and this makes it far from trivial to assess which is the kinetically preferred site of protonation. − It is commonly considered that proton transfers at carbon sites or at metal centers are intrinsically slow because of the considerable geometric and electronic rearrangements that arise as a consequence of the protonation event and that protonation of a hydrido ligand may be kinetically preferred because the accompanying structural/electronic changes are less significant. − The protonation process described herein appears to be rather fast for a well-documented 15 metal-centered process and is characterized by a low activation enthalpy. The large negative value for the activation entropy and the low activation enthalpy strongly suggest that the observed process has an associative character and is in agreement with the addition of a proton and MeCN, formally an oxidative addition process.…”

{Bis[2-(diphenylphosphino)ethyl]phenylphosphine-κ3P,P′,P′′}chloridopalladium(II) hexafluoridophosphate

“…The corresponding complexes with both Pt II and Pd II have been previously reported as chloride and diphenyltetrachloridostannate(IV) salts (Sevillano et al, 1999a;Garcia-Seijo et al, 2001;Housecroft et al, 1990). For other group 10-triphos complexes, see: Sevillano et al (1999b); Fernadez et al (2005); Aizawa et al (2002); Bertinsson et al (1983); Autissier et al (2005); Fernandez et al (2005).…”

{Bis[2-(diphenylphosphino)ethyl]phenylphosphine-κ3P,P′,P′′}chloridoplatinium(II) hexafluoridophosphate

“…The corresponding complexes with both Pt II and Pd II have been previously reported as chloride and diphenyltetrachloridostannate(IV) salts (Sevillano et al, 1999a;Garcia-Seijo et al, 2001;Housecroft et al, 1990). For other group 10-triphos complexes, see: Sevillano et al (1999b); Mü ller et al 2000; Aizawa et al (2002); Bertinsson et al (1983); Autissier et al (2005); Fernandez et al (2005); King et al (1971). Table 1 Selected bond lengths (Å ).…”