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Salt-free Reducing Reagent of Bis(trimethylsilyl)cyclohexadiene Mediates Multielectron Reduction of Chloride Complexes of W(VI) and W(IV)

Salt-free Reducing Reagent of Bis(trimethylsilyl)cyclohexadiene Mediates Multielectron Reduction of Chloride Complexes of W(VI) and W(IV)

Hayato Tsurugi, Hiromasa Tanahashi, Haruka Nishiyama, Waldemar Fegler, Teruhiko Saito, Andreas Sauer, Jun Okuda, Kazushi Mashima

J Am Chem Soc. 2013 Apr 24;135(16):5986-9.

PMID: 23581394

Abstract:

We developed a salt-free reduction of WCl6 using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) in toluene to give a low-valent trinulcear tungsten complex involving W(II) and W(III) centers, while in the presence of redox active ligands such as α-diketone and α-diimine the same reduction produced W(IV) complexes with the corresponding redox-active ligands, (α-diketone)WCl4 and (α-diimine)WCl4. A W(VI) complex with two α-diketone ligands, (α-diketone)2WCl2, was found to be synthetically equivalent to low-valent W(IV) species that trapped azopyridine to give (α-diketone)WCl2(azopyridine).

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13470138	Tungsten(IV) chloride		13470-13-8	Price
AP70969298	Bis(trimethylsilyl)amidohafnium(IV) chloride		70969-29-8	Price

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