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- Title
Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)methanide Ligands.
- Authors
Haehnel, Martin; Hansen, Sven; Priebe, Jacqueline B.; Spannenberg, Anke; Arndt, Perdita; Brückner, Angelika; Rosenthal, Uwe
- Abstract
A study of the coordination chemistry of different bis(diphenylphosphino)methanide ligands [Ph2PC(X)PPh2] (X=H, SiMe3) with Group 4 metallocenes is presented. The paramagnetic complexes [Cp2Ti{κ2- P, P-Ph2PC(X)PPh2}] (X=H ( 3 a), X=SiMe3 ( 3 b)) have been prepared by the reactions of [(Cp2TiCl)2] with [Li{C(X)PPh2}2(thf)3]. Complex 3 b could also be synthesized by reaction of the known titanocene alkyne complex [Cp2Ti(η2-Me3SiC2SiMe3)] with Ph2PC(H)(SiMe3)PPh2 ( 2 b). The heterometallacyclic complex [Cp2Zr(H){κ2- P, P-Ph2PC(H)PPh2}] ( 4 aH) has been prepared by reaction of the Schwartz reagent with [Li{C(H)PPh2}2(thf)3]. Reactions of [Cp2HfCl2] with [Li{C(X)PPh2}2(thf)3] gave the highly strained corresponding metallacycles [Cp2M(Cl){κ2- P, P-Ph2PC(X)PPh2}] ( 5 aCl and 5 bCl) in very good yields. Complexes 3 a, 4 aH, and 5 aCl have been characterized by X-ray crystallography. Complex 3 a has also been characterized by EPR spectroscopy. The structure and bonding of the complexes has been investigated by DFT analysis. Reactions of complexes 4 aH, 5 aCl, and 5 bCl did not give the corresponding more unsaturated heterometallacyclobuta-2,3-dienes.
- Subjects
METALLOCENES; LIGANDS (Chemistry); DIPHENYLPHOSPHINE; ALKYNES; METALLACYCLES; ELECTRON paramagnetic resonance spectroscopy
- Publication
Chemistry - A European Journal, 2013, Vol 19, Issue 23, p7568
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201300218