Photochemische Aren-Substitution in Cyclopentadienyleisen-Aren-Kationen—Eine allgemeine Synthese für Cyclopentadienyleisen-Bisphosphin-Ligand-Komplexe mit Liganden der 4. und 5. Hauptgruppe

Iron complexes of facially capping triphosphorus macrocycles

“…This journal is © The Royal Society of Chemistry 2006 3), 89.67 (12); P(2)-Fe(1)-P(1), 89.78 (12); P(3)-Fe(1)-P(1), 91.78 (11).…”

“…Of interest in this context are complexes of the form [(g 5 -Cp R )FeL 3 ] + (R = various alkyl/silyl combinations) for which the syntheses and reactivities have been extensively studied and there are numerous examples of analogous complexes containing tertiary mono-phosphines, 8 diphosphines, 9 triphosphines, 10 and phosphite ligands. 11 These complexes appear to offer advantages over previous templates based upon M(CO) 3 (M = Cr, Mo, W) units; three features are of particular interest to us. Firstly, variations in cyclopentadienyl ring substituents are readily achieved and introduce the opportunity to vary the solubility of template precursors as well as the steric influence over the trans reaction sites (e.g.…”

Template synthesis of benzannulated triphosphacyclononanes—a new class of phosphacrowns via template assisted nucleophilic P–C bond formation

“…The Fe-P bond lengths are 2.156(1) s (average, to the P-atoms with an o-C 6 H 4 F substituent) and 2.180(1) s (to the P-atom with the phenyl group), indicating that back-bonding from the CpFe + fragment is still significant. The average Fe-P bond length in the cation CpFe(P(OMe) 3 ) 3 + is 2.144 s. 11 We have reported recently the crystal structure of a Cp*Fe complex of 1,4,7-triethyl-1,4,7-triphosphacyclononane, 4b which shows fairly similar bond angles around the central atom but the average Fe-P bond length in this complex (with an aliphatic backbone) is significantly longer than in 4 at 2.192 s. Thus, the present macrocycle appears to be a better donor. The rigid 5-membered chelate rings force all P-Fe-P angles to be around 86u, significantly less than the ideal octahedral angle of 90u.…”

“…The coordinated acetonitrile is then exchanged with phenylphosphine by gentle heating in 1,2-dichloroethane, yielding compound 3, following a previously reported route to mixed CpFe-biphosphine-monophosphine complexes. 11 Again, upon coordination the signal for the primary phosphine is shifted around 115 ppm downfield (the chemical shift of free phenylphosphine is 2123 ppm) in the 31 P{ 1 H}-NMR spectrum, which appears as an A 2 X pattern of a doublet and triplet assigned to the coordinated tertiary and primary phosphines respectively; the latter is further split into a triplet of doublets in the proton-coupled 31 P-NMR spectrum. The IR spectrum shows the disappearance of the band attributable to n (CN) and the presence of a band attributable to n (PH) .…”

Photochemical replacement of benzene in the tetramethylcyclopentadienyl complex of iron, [η-C5Me4H)Fe(η-C6H6)]+

“…Reactions of cation 1 with phosphites P(OR) 3 19 The stronger coordination of the σ ligands to the Fe atom in the tetramethylcyclopenta dienyl complexes is probably due to the stronger electron donating properties of the C 5 Me 4 H ligand compared to Cp, C 6 H 7 , and 9 SMe 2 7,8 C 2 B 9 H 10 .…”