NDLI: A crystallographic and spectroscopic study on the reactions of $WCl

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Dolci, Sara Marchetti, Fabio Pampaloni, Guido Zacchini, Stefano
Description	Author Affiliation: Dolci S ( University of Pisa, Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, I-56126 Pisa, Italy.)
Abstract	$WCl_{6},$ 1, reacted with two equivalents of $HC(O)NR_{2}$ (R = Me, Et) in $CH_{2}Cl_{2}$ to afford the W(VI) oxo-derivatives $WOCl_{4}(OCHNR_{2})$ (R = Me, 2a; R = Et, 2b) as main products. The hexachlorotungstate(V) salts $[\{O=C–N(Me)CH_{2}CH_{2}CH_{2}\}_{2}(μ-H)][WCl_{6}],$ 3, and $[PhNHC(Me)N(Ph)C(O)Me][WCl_{6}],$ 4, were isolated in moderate yields from the 1:2 molar reactions of 1 with N-methyl-2-pyrrolidone (in $CH_{2}Cl_{2})$ and acetanilide (in CDCl $_{3}$ ), respectively. The additions of two equivalents of ketones / aldehydes to $1/CH_{2}Cl_{2}$ yielded the complexes $WOCl_{4}[OC(R)(R′)]$ (R = Me, R′ = Ph, 5a; R = R′ = Ph, 5b; R = R′ = Me, 5c; R = R′ = Et, 5d; R = H, R′ = $2-Me-C_{6}H_{4},$ 5e) and equimolar amounts of $C(R)(R′)Cl_{2}.$ Analogously, $WOCl_{3}[κ^{2}-\{1,2-C_{6}H_{4}(O)(CHO)\}],$ 5f, and $1,2-C_{6}H_{4}(OH)(CHCl_{2})$ were obtained from 1 and salicylaldehyde . The 1:1 reaction of 1 with acetone in $CH_{2}Cl_{2}$ resulted in the clean formation of $WOCl_{4}$ and 2,2-dichloropropane . Compounds 5a,b,f were isolated as crystalline solids, whereas 5c,d,e could be detected by solution NMR only. The interaction of $1/CH_{2}Cl_{2}$ with isatin , in a 1:1 molar ratio, revealed to be a new, convenient route for the synthesis of 3,3-dichloro-2,3-dihydro-1 H-indol-2-one , 6. The 1:1 reactions of 1 with $R′OCH(R)CO_{2}Me$ (R = H, R′ = Me; R = Me, R′ = H) in a chlorinated solvent afforded the tungsten(V) adducts $WCl_{4}[κ^{2}-OCH(R)CO_{2}Me]$ (R = H, 7a; R = Me, 7b). $1/CH_{2}Cl_{2}$ reacted sluggishly with equimolar quantities of $trans-(CO_{2}Et)CH=CH(CO_{2}Et)$ and $CH_{2}(CO_{2}Me)_{2}$ to give, respectively, the W(IV) derivatives $WCl_{4}[κ^{2}-CH_{2}(CO_{2}Me)_{2}],$ 8a, and $[WCl_{4}-κ^{2}-\{trans-(CO_{2}Et)CH=CH$ $(CO_{2}Et)\}]_{n},$ 8b, in about 70% yields. The molecular structures of 2a, 3, 4, 5a, 5f, 7a and 7b were ascertained by X-ray diffraction studies.
ISSN	14779226
Issue Number	16
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-04-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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