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

Herein, we report the syntheses of the novel P(O)(O i Pr) 2 ‐ and organostannyl‐substituted 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 }] ( 1a ), Fe[η 5 ‐C 5 H 3 ‐1‐SnPh 3 ‐2‐P(O)(O‐ i Pr) 2 ] 2 ( 1b ), Fe[{η 5 ‐C 5 H 2 ‐1,3‐(SnPh 2 X) 2 ‐2‐P(O)(O i Pr) 2 }{η 5 ‐C 5 H 4 P(O)(O i Pr) 2 }] ( 2 , X = I; 3 , X = Br; 4 , X = Cl; 5 , X = F), and η 5 ‐CpFeη 5 ‐C 5 H‐1,3‐(SnPh 3 ) 2 ‐4,5‐[P(O)(O i Pr) 2 ] 2 ( 7 ). Furthermore, we report the synthesis of the organotin iodide η 5 ‐CpFeη 5 ‐C 5 H‐1,3‐(SnPh 2 I) 2 ‐4,5‐[P(O)(O i Pr) 2 ] 2 ( 8 ), and its reactions with KF, AgPF 6 , I 2 , and AgClO 4 to provide the corresponding organotin derivatives η 5 ‐CpFeη 5 ‐C 5 H‐1,3‐(SnPh 2 I) 2 ‐4,5‐[P(O)(O i Pr) 2 ] 2 ( 9 ), η 5 ‐CpFeη 5 ‐C 5 H‐1,3‐(SnPhI 2 ) 2 ‐4,5‐[P(O)(O i Pr) 2 ] 2 ( 10 ), and [η 5 ‐CpFeη 5 ‐(C 5 H‐1‐SnPh 2 OH‐3‐SnPh 2 ‐4,5‐{P(O)(O i Pr) 2 } 2 )]ClO 4 · H 2 O ( 11 ). The latter compound is the first example of an air‐stable, tetrasubstituted ferrocene derivative containing a bicentric (bis)organotin cation. The compounds were characterized by elemental analysis, 1 H, 13 C, 31 P, 119 Sn NMR and IR spectroscopy, electrospray ionization mass spectrometry, and, except for 6 and 9 , single‐crystal X‐ray diffraction analysis.