1. Synthesis and reactivity of cyclam-based Zr(IV) complexes.
- Author
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Alves, Luis G., Munhá, Rui F., and Martins, Ana M.
- Subjects
- *
SILVER salts , *ZIRCONIUM compounds , *ZIRCONIUM - Abstract
Graphical abstract Highlights • Trans-disubstituted diamido diamine cyclams support cationic zirconium complexes. • (Bn 2 Cyclam)ZrCl 2 reacts with silver salts to form either neutral or cationic species. • (Bn 2 Cyclam)Zr(C 6 F 5) 2 displays a fluxional behaviour in solution. • (Bn 2 Cyclam)ZrCl} 2 (k 2- N,N' -Bn 2 Cyclam) displays one terminal- and one bridging- cyclam. • [(ansa -η5:η5-Cp 2 CMe 2)ZrCl(HBn 2 Cyclam)] is the first mixed cyclam/cyclopentadienyl complex. Abstract (Bn 2 Cyclam)ZrCl 2 reacts with silver salts to form either neutral or cationic species depending on the nature of the counterion. The reaction of (Bn 2 Cyclam)ZrCl 2 with AgCF 3 COO affords (Bn 2 Cyclam)Zr(OCOCF 3) 2 while with AgPF 6 the cationic species [(Bn 2 Cyclam)ZrCl(CH 3 CN)]PF 6 is formed. Cations of formulas [(All 2 Cyclam)ZrX(L)]+ (X = Me, L = CD 2 Cl 2 ; X, L = η2-CH 2 Ph), [(MeAll 2 Cyclam)Zr(η2-CH 2 Ph)]+ and [(Bn 2 Cyclam)Zr(n Bu)(THF)]+ were prepared by abstraction of one alkyl ligand from (R 2 Cyclam)ZrX 2 (R = All, MeAll, Bn; X = Me, CH 2 Ph, n Bu) using B(C 6 F 5) 3 or [PhMe 2 NH][B(C 6 F 5) 4 ]. (Bn 2 Cyclam)Zr(C 6 F 5) 2 was obtained by reaction of (Bn 2 Cyclam)ZrCl 2 with 2 equiv. of MgBrC 6 F 5. The complex (Bn 2 Cyclam)ZrCl} 2 (k 2- N,N' -Bn 2 Cyclam) displaying a cyclam bridging ligand was obtained either from the 1:1 reaction of (Bn 2 Cyclam)ZrCl 2 with LiNiPr 2 and from the reaction of 2 equiv. of (Bn 2 Cyclam)ZrCl 2 with Li 2 (Bn 2 Cyclam).(THF) 2 in THF. The reaction of LiCpC(Me) 2 CpLi with (Bn 2 Cyclam)ZrCl 2 led to the formation of the mixed cyclam/cyclopentadienyl complex [(ansa -η5:η5-Cp 2 CMe 2)ZrCl(HBn 2 Cyclam)]. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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