Synthesis of labeled metallocenes via double Π‐ligand transfer

Abstract

:Labeled ruthenocenes were prepared by heating substituted ferrocenes with lo3RuC13 involving (7f'-ligandl-( ,T'-ligand l exchange.Coproportionation and disproportionation of a mixture of a radioactive metallocene compound and an inactive one in the presence of catalytic amounts of FeC13 or RuC13 provided a variety of labeled metallocenes in a simple one step procedure.

Preparation of Cyclopentadienyltricarbonylrhenium Complexes Using a Double Ligand-Transfer Reaction

“…The reagents that inhibited the transformation likely underwent nonproductive side reactions. For instance, it is known that RuCl 3 reacts with ferrocene to produce ruthenocene. , This could inhibit ring transfer to rhenium, as ruthenocene is thermodynamically more stable than ferrocene. , …”

“…With respect to the second ligand transfer, that of the Cp ring from iron to rhenium, there is considerable literature precedent for AlCl 3 -induced Fe−Cp bond breakage but these reactions generally involve Cp ring replacement by an arene (e.g. benzene) − or ring interchange between differentially substituted ferrocene molecules. − Outside of the DLT reaction, the only example of Cp ring transfer from ferrocene to another metal is the reaction of ferrocene with RuCl 3 to produce ruthenocene. , …”

Synthesis of 17?-ruthenocenyl-17?-oestradiol and its potential as a radiopharmaceutical agent

“…With this in mind, attempts can be made to synthesize new radioactive ruthenium compounds. [16][17][18][19][20][21]…”

“…It has been suggested that the affinity marking property of organometallic hormones is due to the action of carbenium ions generated from Ϫ 0.316(1) 0.0955(9) 0.9126 (7) 0.0480 C (4) Ϫ 0.229(1) 0.221(1) 0.775(1) 0.0304 C (5) Ϫ 0.195(1) 0.242(1) 0.669(1) 0.0300 C (6) Ϫ 0.137(2) 0.358(1) 0.640(1) 0.0430 C (7) Ϫ 0.064(2) 0.360(1) 0.533(1) 0.0406 C (8) Ϫ 0.159(2) 0.299(1) 0.441(1) 0.0320 C (9) Ϫ 0.167(1) 0.173(1) 0.4742 (9) 0.0338 C (10) Ϫ 0.223(1) 0.159(1) 0.587(1) 0.0246 C (11) Ϫ 0.254(2) 0.106(1) 0.379(1) 0.0418 C (12) Ϫ 0.182(2) 0.115(1) 0.272(1) 0.0443 C (13) Ϫ 0.174(2) 0.242(1) 0.239(1) 0.0292 C (14) Ϫ 0.083(1) 0.306(1) 0.335(1) 0.0273 C (15) Ϫ 0.059(2) 0.421(1) 0.285(1) 0.0461 C (16) Ϫ 0.034(2) 0.397(1) 0.164(1) 0.0426 C (17) Ϫ 0.075(1) 0.269(1) 0.146(1) 0.0353 O (17) Ϫ 0.152(1) 0.2563(9) 0.0368 (7) 0.0459 C (18) Ϫ 0.328(1) 0.296 (2) Table 5 shows the results obtained.…”

“…In fact, the derivatives of ruthenocene containing [ 97 Ru] or [ 103 Ru] offer 'the desirable stable combination of a ␥-emitter tightly bound to an aromatic organic moiety capable of considerable variation'. 15 Curiously, despite its potential and the pioneering work of Wenzel, [16][17][18][19] the radiochemistry of organometallic compounds 20 has undergone very little development in recent years, 21 owing to the difficulty in finding a stable combination of a ␥emitter and an organic vector with specific activity for a target organ.…”