om201220w_si_002.pdf (416.08 kB)
Synthesis, Electrochemistry, Spectroelectrochemistry, and Solid-State Structures of Palladium Biferrocenylphosphines and Their Use in C,C Cross-Coupling Reactions
journal contribution
posted on 2012-03-26, 00:00 authored by Manja Lohan, Bianca Milde, Silvio Heider, J. Matthäus Speck, Sabrina Krauße, Dieter Schaarschmidt, Tobias Rüffer, Heinrich LangThe series of biferrocenyl-functionalized phosphines
Bfc(PR2)/Bfc(SePR2) (R = C6H5 (6/14), C6H4-2-CH3 (7/15), cC4H3O (8/16), cC6H11 (9/17); Bfc = 1′-biferrocenyl,
Fe(η5-C5H5)(η5-C5H4)Fe(η5-C5H4)2) and biferrocenyl diphosphines bfc(PR2)2/bfc(SePR2)2 (R = C6H5 (10/18), C6H4-2-CH3 (11/19), cC4H3O (12/20), cC6H11 (13/21); bfc = 1′,1‴-biferrocenyl, (Fe(η5-C5H4)2)2) have
been prepared by consecutive synthesis methodologies. The reaction
of 6–9 with [Pd(Et2S)2Cl2] (22) gave the appropriate palladium
dichloride complexes trans-[Pd(Bfc(PR2))2Cl2] (R = C6H5 (23), C6H4-2-CH3 (24), cC4H3O (25), cC6H11 (26)). The structures
of 15, 16, 21, 23, and 25 in the solid state were determined by single-crystal
X-ray diffraction studies, showing that the structural parameters
of these molecules correspond to those of related seleno phosphines
and phosphino palladium dichloride complexes. Additionally, all complexes
were characterized by cyclic voltammetry using [nBu4N][PF6] and [nBu4N][B(C6F5)4]
as supporting electrolytes. Phosphines 6–9 and seleno phosphines 14–17 show mostly irreversible redox processes involving the phosphorus
and the selenium atom, both being able to form radicals leading to
dimerization and other follow-up reactions. In contrast, palladium
complexes 23–26 show in both electrolyte
solutions a reversible behavior, although the iron centers were oxidized
at more positive potentials in comparison to free Bfc or bfc phosphines.
UV/vis/near-IR spectroelectrochemical measurements were carried out
with 25 and 26. At potentials between 300
and 700 mV IVCT bands typical for [Bfc]+ are observed,
reflecting intermetallic communication between the two ferrocene moieties
within the biferrocenyl phosphine units, two of which are present.
No further bands were found, indicating that no electronic communication
between the biferrocenyl moieties along the P–Pd–P unit
exists in the mixed-valent species. The palladium complexes are suitable
catalysts in the Suzuki reaction of 2-bromotoluene (27) or 4′-chloroacetophenone (28) with phenylboronic
acid (29). They can also be applied in the Heck C,C cross-coupling
of iodobenzene (32) with tert-butyl
acrylate (33). Depending on the steric (estimated by
the Tolman cone angle) and electronic properties (estimated by 1J31P77Se) of the phosphine ligands, the activity of the corresponding palladium
complexes can be predicted. It was found that bulky and electron-rich
cyclohexyl- and o-tolyl-containing complexes are
the most active catalysts in the appropriate Suzuki and Heck reactions.