RESUMEN
A revised in situ base mechanism of alkyne alkoxycarbonylation via a Pd catalyst with hemilabile P,N-ligands (PyPPh2, Py = 2-pyridyl) has been fully characterised at the B3PW91-D3/PCM level of density functional theory. Key intermediates on this route are acryloyl and η3-propen-1-oyl complexes that readily undergo methanolysis. With two hemilabile P,N-ligands and one or both of them protonated, the overall computed barrier is 16.8 kcal mol-1. This new mechanism is consistent with all of the experimental data relating to substituent effects on relative reaction rates and branched/linear selectivities, including new results on the methoxycarbonylation of phenylacetylene using (4-Me2N-Py)PPh2 and (6-Cl-Py)PPh2 ligands. This ligand is found to decrease catalytic activity over PyPPh2, thus invalidating a formerly characterised in situ base mechanism.
RESUMEN
Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the electronic ground state of the pentacoordinate cobalt nitrosyl complexes, [CoX2 (NO)(PMePh2 )2 ] (X=Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visible light. Singlet and triplet electron spin states of the complex, corresponding to two different isomers, are populated at room temperature, and the two isomers exchange on a timescale of a few picoseconds. Ultrafast two-dimensional infrared spectroscopy observes the change in wavenumber of the NO ligand band accompanying the isomerization and associated ISC on the (spin) adiabatic ground potential energy surface. Comparison of the dynamics of the chloro- and bromo-complexes shows that inertial effects of the ligand motion have a greater effect than spin-orbit coupling on determining the forward and reverse isomerization and ISC rates.
RESUMEN
The synthesis of a series of CgPAr ligands is reported, where CgP is the 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-6-yl moiety and Ar = 2-pyridyl (L2), 3-pyridyl (L3), 2-pyrimidyl (L4), 4-R-2-pyridyl [R = Me (L5a), CF3 (L6a), SiMe3 (L7a)] or 6-R-2-pyridyl [R = Me (L5b), CF3 (L6b), SiMe3 (L7b). Testing of these ligands in the Pd-catalysed methoxycarbonylation of phenylacetylene reveals that the activity and branched selectivity of the catalysts derived from these ligands varies as a function of the N-heterocycle, with the catalyst derived from L5b being the most active of those tested. This, together with the poor performance of catalysts derived from L3 supports the hypothesis that the catalysis proceeds by a "proton shuttling" mechanism, an idea that previously had only been applied to arylphosphines. Reaction of [PtCl2(cod)] with L where L = L2 or L4-7 yields a rac/meso mixture of the trans-[PtCl2(L)2] (1a-h) complexes, three of which are structurally characterised. 31P NMR spectroscopy shows that reaction of L3 with [PtCl2(cod)] gives a mixture of mononuclear and binuclear metal complexes in solution. The complex trans-[PdCl2(L2)2] (4) reacts with AgBF4 to give the [PdCl(κ1-L2)(κ2-L2)]BF4 (5) with spectroscopic and structural characterisation confirming the presence of a P,N-chelate. 1H and 31P NMR evidence supports the assignment of a pyridyl-protonated species being formed upon treatment of 4 with TsOH·H2O in CD2Cl2; both the protonated species and chelate 5 are observed when the reaction is carried out in MeOH.
RESUMEN
The synthesis of a range of bis(phosphine)boronium salts is reported [(R2HP)2BH2][X] (R = Ph, (t)Bu, Cy) in which the counter anion is also varied (X(-) = Br(-), [OTf](-), [BAr(F)4](-), Ar(F) = 3,5-(CF3)2C6H3). Characterization in the solid-state by X-ray diffraction suggests there are weak hydrogen bonds between the PH units of the boronium cation and the anion (X(-) = Br(-), [OTf](-)), while solution NMR spectroscopy also reveals hydrogen bonding occurs in the order [BAr(F)4](-) < [OTf](-) < Br(-). [(Ph2HP)2BH2][BAr(F)4] reacts with RhH(PPh3)3, by elimination of H2, forming [Rh(κ(1),η-PPh2BH2·PPh2H)(PPh3)2][BAr(F)4] which shows a ß-B-agostic interaction from the resulting base stabilised phosphino-borane ligand. Alternatively such ligands can be assembled directly on the metal centre by reaction of in situ generated {Rh(PPh3)3}(+) and Ph2HP·BH3 to afford [Rh(κ(1),η-PPh2BH2·PPh3)(PPh3)2][BAr(F)4], which was characterised by X-ray crystallography. Addition of H3B·PPh2H to the well-defined 16-electron "T-shaped" complex [Rh(P(i)Bu3)2(PPh3)][BAr(F)4] (characterised by X-ray crystallography) formed of a mixture of base-stabilised phosphino borane ligated complexes [Rh(κ(1),η-PR2BH2·PR3)(PR3)2][BAr(F)4] (R = (i)Bu or Ph). These last observations may lend clues to the formation of bis(phosphine)boronium salts in the catalytic dehydrocoupling reaction of phosphine boranes as mediated by Rh(I) compounds.