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Avent AG, Caro CF, Hitchcock PB, et al. Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates. Dalton Trans. 2004;(10):1567-77doi: 10.1039/b316695n.
Avent, A. G., Caro, C. F., Hitchcock, P. B., Lappert, M. F., Li, Z., & Wei, X. H. (2004). Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates. Dalton transactions (Cambridge, England : 2003), (10), 1567-77. https://doi.org/10.1039/b316695n
Avent, Anthony G, et al. "Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates." Dalton transactions (Cambridge, England : 2003) vol. ,10 (2004): 1567-77. doi: https://doi.org/10.1039/b316695n
Avent AG, Caro CF, Hitchcock PB, Lappert MF, Li Z, Wei XH. Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates. Dalton Trans. 2004 May 21;(10):1567-77. doi: 10.1039/b316695n. Epub 2004 Apr 21. PMID: 15252606.
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Dalton Trans. 2004 May 21;(10):1567-77. doi: 10.1039/b316695n. Epub 2004 Apr 21.

Synthetic and structural experiments on yttrium, cerium and magnesium trimethylsilylmethyls and their reaction products with nitriles; with a note on two cerium beta-diketiminates.

Dalton transactions (Cambridge, England : 2003)

Anthony G Avent, Catherine F Caro, Peter B Hitchcock, Michael F Lappert, Zhengning Li, Xue-Hong Wei

Affiliations

  1. The Chemistry Laboratory, University of Sussex, Brighton, UK BN1 9QJ.

PMID: 15252606 DOI: 10.1039/b316695n

Abstract

The yttrium, cerium and magnesium bis(trimethylsilyl)methyls [Ln[CH(SiMe3)2]3][Ln = Y (1), Ce (2)], and the known compound Mg[[CH(SiMe3)2]2 (C) and [Mg(mu-Br)[CH(SiMe3)2](OEt2)]2 (D) formed the crystalline nitrile adducts [1(NCBut)2] (5), [2(NCPh)] (6), [C(NCR)2][R = But (8), Ph (9), C6H3Me2-2,6 (10)] and [Mg(mu-Br)[CH(SiMe3)2](NCR)]2 [R = But (11), Ph (12), C6H3Me2-2,6 (13)], rather than beta-diketiminato-metal insertion products. The beta-diketiminato-cerium complex [Ce[(N(SiMe3)C(C6H4But-4))2CH][N(SiMe3)2]2] (16) was obtained from [Ce[N(SiMe3)2]3] and the beta-diketimine H[[N(SiMe3)C(C6H4But-4)]2CH]]. The cerium alkyl 2 and [Ln[CH(SiMe3)(SiMe2OMe)]3][Ln = Y (3), Ce (4)] were obtained from the appropriate lithium alkyl precursor and [Ce(OC6H2But2-2,6-Me-4)3] or LnCl3, respectively. Heating complex 3 with benzonitrile in toluene afforded 2,2-dimethyl-4,6-diphenyl-5-trimethylsilyl-1,3-diaza-2-silahexa-1,3-diene (7), a member of a new class of heterocycles. The X-ray structures of the crystalline compounds, D, [Mg[CH(SiMe3)2]2(OEt2)2], the known [Ce(Cl)[(N(SiMe3)C(Ph))2CH]2] (E) and 16 are reported. The cerium alkyl (like 1) has one close Ce...C contact for each ligand, attributed to a gamma-C-Ce agostic interaction. The Ln alkyls and have a trigonal prismatic arrangement of the chelating ligands (each of the same chirality at Calpha) around the metal. In an arene solution at 313 K exists as two isomers, as evident from detailed NMR spectroscopic experiments.

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