Side-On Bound Dinitrogen Complex of Zirconium Supported by a P 2 N 2 Macrocyclic Ligand
2008; American Chemical Society; Volume: 47; Issue: 4 Linguagem: Inglês
10.1021/ic701599t
ISSN1520-510X
AutoresL. Morello, M.J. Ferreira, Brian O. Patrick, Michael D. Fryzuk,
Tópico(s)Metalloenzymes and iron-sulfur proteins
ResumoReduction of [P 2N 2]ZrCl 2 (where P 2N 2 = PhP(CH 2SiMe 2NSiMe 2CH 2) 2PPh) by KC 8 under N 2 generates the dinuclear dinitrogen complex ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2) and impurities in varying yields depending on the solvent and temperature. The toluene complex [P 2N 2]Zr(eta (6)-C 7H 8) along with a dinuclear species with bridging PC 6H 5 groups is observable. Also observable in the crude reaction mixtures is the mu-oxodiazenido derivative, ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2H 2)(mu-O), due to reaction with trace H 2O. This paper reports the full details of the preparation of ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2) including an improved method that involves reduction at low temperatures in a tetrahydrofuran solvent. Also reported is a reproducible synthesis of the oxodiazenido complex along with the X-ray structures of the dinitrogen complex and the oxodiazenido derivative.
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