Dimethyltin(IV) bis(3,5-diphenylpyrazolate) as a synthetic reagent in the preparation of rare-earth pyrazolate complexes

Beaini, Samar, Deacon, Glen B., Delbridge, Ewan, Junk, Peter C., Skelton, Brian W., and White, Allan H. (2008) Dimethyltin(IV) bis(3,5-diphenylpyrazolate) as a synthetic reagent in the preparation of rare-earth pyrazolate complexes. European Journal of Inorganic Chemistry, 2008 (29). pp. 4586-4596.

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Abstract

Reaction of SnMe2Cl2 with [Li(Ph2pz)] (Ph2pz = 3,5-diphenylpyrazolate) in diethyl ether in a 1:2 ratio afforded the new transmetallation reagent [SnMe2(Ph2pz)2]. Treatment of [SnMe2(Ph2pz)2] with Ln metals in either 1,2-dimethoxyethane (dme) or tetrahydrofuran (thf) provided a new route to the divalent [Ln(Ph2pz)2(dme)2] (Ln = Sm, Eu, Yb) and the trivalent [La(Ph2pz)3(dme)2] and [Yb(Ph2pz)3(thf)2] complexes in comparable yields to those from alternative methods. These reactions enabled isolation of the highly reactive [Sm(Ph2pz)2(dme)2] complex in good yield, in addition to the new cis isomer of [Eu(Ph2pz)2(dme)2], thereby establishing a rare case of geometric isomerism in lanthanoid chemistry. 1H and 119Sn NMR spectral studies and EDAX measurements were performed on the reaction mixture and/or residue to identify the tin-containing products and suggest formation of SnMe4, Sn2Me6, tin metal and two other SnMe3 species, which plausibly result from decomposition of unstable "SnMe2". Treatment of [Yb(Ph2pz)2(dme)2] with [SnMe2(Ph2pz)2] or [Tl(Ph2pz)] resulted in the isolation of [Yb(Ph2pz)3(thf)2]·2C6D6 and [Yb(Ph2pz)3(dme)]·0.5dme complexes, the structures of which have eight-coordinate Yb atoms and contrast nine-coordination observed for previous [Ln(Ph2pz)3(thf or dme)n] complexes.

Item ID: 29626
Item Type: Article (Refereed Research - C1)
Keywords: redox transmetallation, lanthanoids, dimethyltin reagents, organotin(IV), pyrazolate, rare-earth elements
ISSN: 1099-0682
Funders: Australian Research Council (ARC), Monash University: Postgraduate Publications Award
Date Deposited: 02 Oct 2013 10:34
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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