| Autor: |
Kornev AN; Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinin Street, 603950 Nizhny Novgorod, Russia. akornev@iomc.ras.ru, Sushev VV, Panova YS, Belina NV, Lukoyanova OV, Fukin GK, Ketkov SY, Abakumov GA, Lönnecke P, Hey-Hawkins E |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2012 Jan 16; Vol. 51 (2), pp. 874-81. Date of Electronic Publication: 2011 Dec 30. |
| DOI: |
10.1021/ic201617p |
| Abstrakt: |
Reactions of diphosphinohydrazines R-NH-N(PPh(2))(2) (R = tBu (1), Ph(2)P (3)) with some metalation reagents (Co[N(SiMe(3))(2)](2), LiN(SiMe(3))(2), La[N(SiMe(3))(2)](3), nBuLi, MeLi) were performed. Compound 1 was synthesized by the reaction of Ph(2)PCl with tert-butylhydrazine hydrochloride in 83% yield. This compound reveals temperature-dependent (31)P NMR spectra due to hindered rotation about the P-N bonds. Complicated redox reaction of 1 with Co[N(SiMe(3))(2)](2) proceeds with cleavage of the P-N and N-N bonds to form a binuclear cobalt complex [Co{HN(PPh(2))(2)-κ(2)P,P'}(2)(μ-PPh(2))](2) (2) demonstrating a short Co···Co distance of 2.3857(5) Å, which implies a formal double bond between the Co atoms. Strong nucleophiles (nBuLi, MeLi) cause fragmentation of the molecules 1 and 3, while reactions of 3 with lithium and lanthanum silylamides give products of the NNP → NPN rearrangement [Li{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}(THF)(2)] (4) and [La{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}{N(SiMe(3))(2)}(2)] (5), respectively. These complexes represent the first examples of a κ(2)N,N' bonding mode for the triphosphazenide ligand [(Ph(2)PN)(2)PPh(2)](-). DFT calculations showed large energy gain (52.1 kcal/mol) of the [NNP](-) to [NPN](-) anion rearrangement. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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