Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands. Issue 25 (23rd May 2014)

• Record Type: Journal Article
• Authors: Haehnel, Martin; Priebe, Jacqueline B.; Yim, Jacky C.‐H.; Spannenberg, Anke; Brückner, Angelika; Schafer, Laurel L.; Rosenthal, Uwe
• Is Part Of: Chemistry. Volume 20:Issue 25(2014)
• Page Start: 7752
• Page End: 7758
• Publication Date: 2014-05-23
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402571
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A study of the coordination chemistry of different amidato ligands [(R)NC(Ph)O] (R=Ph, 2, 6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp<sub>2</sub>M(Cl){κ<sup>2</sup>‐<italic>N</italic>, <italic>O</italic>‐(R)NC(Ph)O}] M=Zr, R=Dipp (<bold>1 a</bold>), Ph (<bold>1 b</bold>); M=Hf, R=Ph (<bold>2</bold>)) were synthesized by reaction of [Cp<sub>2</sub>MCl<sub>2</sub>] with the corresponding deprotonated amides. Complex <bold>1 a</bold> was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp<sub>2</sub>Zr(H)Cl]. Salt metathesis reaction of [Cp<sub>2</sub>Zr(H)Cl] with deprotonated amide [(Dipp)NC(Ph)O] gave the zirconocene hydrido complex [Cp<sub>2</sub>M(H){κ<sup>2</sup>‐<italic>N</italic>, <italic>O</italic>‐(Dipp)NC(Ph)O}] (<bold>3</bold>). Reaction of <bold>1 a</bold> with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)<sub>3</sub>Mg(Cl) {κ<sup>2</sup>‐<italic>N</italic>, <italic>O</italic>‐(Dipp)NC(Ph)O}] (<bold>4</bold>; py=pyridine). The paramagnetic complexes [Cp′<sub>2</sub>Ti{κ<sup>2</sup>‐<italic>N</italic>, <italic>O</italic>‐(R)NC(Ph)O}] (Cp′=Cp, R=Ph (<bold>7 a</bold>); Cp′=Cp, R=Dipp (<bold>7 b</bold>); Cp′=Cp*, R=Ph (<bold>8</bold>)) were prepared by the reaction of the known titanocene alkyne complexes [Cp<sub>2</sub>′Ti(η<sup>2</sup>‐Me<sub>3</sub>SiC<sub>2</sub>SiMe<sub>3</sub>)] (Cp′=Cp (<bold>5</bold>), Cp′=Cp* (<bold>6</bold>)) with the corresponding amides. Complexes <bold>1 a</bold>, <bold>2</bold>, <bold>3</bold>, <bold>4</bold>, <bold>7 a</bold>, <bold>7 b</bold>, and <bold>8</bold> were characterized by X‐ray crystallography. The structure and bonding of complexes <bold>7 a</bold> and <bold>8</bold> were also characterized by EPR spectroscopy.</p> </abstract>