Neue hyperkoordinierte Organozinnverbindungen mit Ferrocenyl-, Zangen- und Benzylphosphinoxid- Substituenten

摘要

Ferrocene is among the most spectacular organometallic compounds ever repoted. [1] Even 60 years after the invention of ferrocene the scientific interest is stillunbroken. One reason for the popularity is the planar chirality of 1,2 or 1,3 disubstitutedferrocenes.This work will focus on the 1,2disubstitutedferrocenes, which are generally prepared from the corresponding monosubstitutedferrocene via an intramolecularly donor group directed ortho-metalation. [6] The preparation of phosphorous containing monosubstiutedferrocenes is the first part of this work. Via monolithiationof ferrocene followed by an electrophile substitution it was possible to synthesize FcP(O)(O-iPr)21, FcP(O)Ph2[7b ]2, FcPPh23undFcP(S)Ph2 [7c] 4. Their ortholithiation (compound 1,2) and treatment with Ph3SnCl provided the corresponding organotin compounds [FcP(O)(O-iPr)2] SnPh35 and [FcP(O)Ph2] SnPh36. Further on the reactivity of compound 5 towards halogens were investigated, via the reaction of 5 with elementary Iodine, Bromine and HCl to provide the corresponding organotinhalides: FcP(O)(O-iPr)2SnPh2I 7, FcP(O)(O-iPr)2SnPh2Br 8, FcP(O)(O-iPr)2SnPh2Cl9. The corresponding fluoride10 was achieved by the reaction of9 with KF. DFT calculations revealed that the positive charge located at the tin atom decrease towards higher atomic number. In the same way it was possible to synthesize FcP(O)(O-iPr)2SnPh1Br2 13 ,FcP(O)(O-iPr)2SnPh1I211, FcP(O)(O-iPr)2SnI3 12. The reaction of organotiniodides with perchlorate gave the corresponding organotin salts FcP(O)(O-iPr)2SnPh2(ClO4) 17 und FcP(O)(O-iPr)2SnPhI(ClO4) 18. The configuration of the diastereomer18 is SP-R. Interestingly the reaction with two equivalents of perchlorate gives the organotinstannol FcP(O)(O-iPr)SnPh(ClO4)20, which crystalizes as a dimer. To go on with my diploma thesis I tried to enhance the crystallographic behavior of the heteroleptic stannylene 4-t-Bu-2-[P(O)(O-i-Pr)2]-6-[P(O)(Ph)(O-i-Pr)] C6H2SnCl 33. Further on it was possible to synthesize the new unsymmetric O.C.O coordinating pincer type ligand 4-t-Bu-2-[P(O)(O-i-Pr)2]-6-[P(O)(t-Bu)(O-i-Pr)] C6H3 40. Starting with o-bromobenzyl bromide the preparation of the organotin fluoride [2-(CH2P(S)Ph2)C6H4]SnPh2F 48 is described.