Different Complexation Behavior of P‐Functionalized Ferrocene Derivatives Towards SnCl₂, SnCl₄ and SnPh₂Cl₂: Auto‐ionization and Redox‐Type Reactions

Abstract

The novel phosphonyl-substituted ferrocene derivatives [Fe(η(5) -Cp)(η(5) -C5 H3 {P(O)(O-iPr)2 }2 -1,2)] (Fc(1,2) ) and [Fe{η(5) -C5 H4 P(O)(O-iPr)2 }2 ] (Fc(1,1') ) react with SnCl2 , SnCl4 , and SnPh2 Cl2 , giving the corresponding complexes [(Fc(1,2) )2 SnCl][SnCl3 ] (1), [{(Fc(1,1') )SnCl2 }n ] (2), [(Fc(1,1') )SnCl4 ] (3), [{(Fc(1,1') )SnPh2 Cl2 }n ] (4), and [(Fc(1,2) )SnCl4 ] (5), respectively. The compounds are characterized by elemental analyses, (1) H, (13) C, (31) P, (119) Sn NMR and IR spectroscopy, (31) P and (119) Sn CP-MAS NMR spectroscopy, cyclovoltammetry, electrospray ionization mass spectrometry, and single-crystal as well as powder X-ray diffraction analyses. The experimental work is accompanied by DFT calculations, which help to shed light on the origin for the different reaction behavior of Fc(1,1') and Fc(1,2) towards tin(II) chloride.

It's Getting Tight: Highly Substituted Intramolecularly P=O→Sn Coordinated Ferrocene Derivatives

“…Fe[{η 5 ‐C 5 H 3 ‐1‐SnPh 3 ‐2‐P(O)(O‐ i Pr) 2 }{η 5 ‐C 5 H 4 P(O)(O‐ i Pr) 2 }] ( C ) and η 5 ‐CpFeη 5 ‐C 5 H 3 ‐1,2‐[P(O)(O‐ i Pr) 2 ] 2 ( D ) were prepared according to literature , …”

“…Selected P(O)(O i Pr) 2 ‐containing complexes A and B containing cationic tin(II) and tin(IV) centers, respectively.…”

“…In continuation of these works in particular, and our general interest in P‐functionalized ferrocene derivatives and their hypercoordinated element compounds we herein study the metalation of the 1,2‐ and 1,1′‐disubstituted ferrocenyl phosphonates mentioned above and present novel intramolecularly P=O→Sn coordinated bis(organostannyl)‐substituted ferrocenes including the only second example of a 1,2,3,4‐tetrasubstituted ferrocene derivative obtained by stepwise metalation, a complete series of the corresponding triorganotin halide derivatives as well as of a ferrocene‐backboned bis(organostannylium) salt.…”

Ferrocenephosphonates: Copper-Promoted Synthesis and Further Functionalization

“…The main approach toward ferrocenephosphonates relies on the reaction of a lithiated ferrocene, prepared either by deprotolithiation using t BuLi, 10 t BuLi- t BuOK mixtures, 11 and the n BuLi·TMEDA chelate 12 or by halogen–lithium exchange, 13 with the required chlorophosphate (Scheme 1 , top). By using these methodologies, a few monosubstituted, 3a c 4 14 1,1′-, 3b,c,5,7a,9a,14c 1,2-, 3c,7b,d and 1,3-disubstituted 15 ferrocenephosphonates have been prepared. Extensions to azaferrocene 16 as well as ruthenocene and biferrocene frameworks 8b have also been documented.…”

A Ferrocenyl-Backboned Unsymmetric O,C-Coordinating Ligand and Its Tin Derivatives

“…In context with our ongoing studies on O,C,O‐coordinating pincer‐type ligands and phosphonyl‐substituted ferrocenes, including their main group element derivatives, as well as with related work by others, we herein present the syntheses and structures of organotin‐substituted derivatives of the recently reported 1,1’‐bis(di iso‐ propoxyphosphonyl) ‐ ferrocene H and the corresponding donor‐stabilized triorganotin cations. To the best of our knowledge, the ionic complexes are, based on 1,1’‐disubstituted ferrocene backboned systems, the first examples, where the metal atom is covalently bound to the cyclopentadienyl ring and donor‐stabilized by P=O moieties.…”