Isocyanate Route to Tungsten(VI) Imido Fluorido Complexes.

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-21 DOI:10.1021/acs.inorgchem.5c03289

Melanie Riethmann,Leonhard Eyßelein,Janis Walpuski,Leon N Schneider,Maik Finze,Udo Radius

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引用次数: 0

Abstract

A general synthetic route for tungsten(VI) organoimido fluorido complexes is reported, which relies on the key metathesis of organo isocyanates and tungsten(VI) oxo tetrafluoride or its acetonitrile adduct [WOF4(MeCN)]. The reaction of 4-tolyl isocyanate, 2,5-dimethylphenyl isocyanate, benzyl isocyanate, 4-fluorophenyl isocyanate and 4-chlorophenyl isocyanate with [WOF4] or [WOF4(MeCN)] at 100 °C in acetonitrile (MeCN) or tetrahydrofuran (THF) afforded the imido complexes [W(NR)F4(L)] (R = Tol = tolyl = 4-CH3-C6H4, 1; DMP = 2,6-dimethylphenyl = 2,6-(CH3)2-C6H3, 2; Bn = benzyl = CH2-C6H5, 3; FPhen = 4-fluorophenyl = 4-F-C6H4, 4; ClPhen = 4-chlorophenyl = 4-Cl-C6H4, 5) as their MeCN or THF adducts 1(MeCN)-5(MeCN) and 1(THF)-5(THF), respectively. Similarly, treatment of [WOF4(MeCN)] with 1,4-phenylene diisocyanate in acetonitrile afforded the dinuclear complex [{WF4(MeCN)}2{μ-1,4-NC6H4N}] (6(MeCN)). The solvent ligand can be easily replaced, as exemplified for the reaction of 1(MeCN), 4(MeCN), and 5(MeCN) with pyridine (py) or 1(MeCN) with benzophenone (PhCOPh) to yield 1(py), 4(py), 5(py) and 1(PhCOPh). Furthermore, 1(MeCN) and 2(MeCN) react with [NMe4]F and NEt3·3HF to yield the tungstate(VI) imido pentafluorido salts [cat][W(NR)F5] (R = Tol, a; DMP; b; cat = NMe4, 7; NEt3H, 8) 7a-8b.

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异氰酸酯制钨（VI）亚酰氟配合物。

报道了一种钨（VI）有机亚胺氟配合物的合成路线，该路线依赖于有机异氰酸酯与四氟化钨（VI）氧或其乙腈加合物[WOF4(MeCN)]的关键复合反应。在乙腈（MeCN）或四氢呋喃（THF）中，4-异氰酸甲酯、2,5-二甲苯基异氰酸甲酯、异氰酸苄酯、4-氟苯基异氰酸甲酯和4-氯苯基异氰酸甲酯与[WOF4]或[WOF4(MeCN)]在100℃下反应得到亚胺配合物[W(NR)F4(L)] (R = Tol = toyl = 4-CH3- c6h4,1; DMP = 2,6-二甲基苯基= 2,6-(CH3)2- c6h3,2；Bn =苄基= CH2-C6H5, 3；FPhen = 4-氟苯基= 4-f - c6h4,4；ClPhen = 4-氯苯= 4- cl - c6h4,5)分别作为它们的MeCN或THF加合物1(MeCN)-5（MeCN）和1(THF)-5（THF）。同样，1,4-苯基二异氰酸酯在乙腈中处理[WOF4(MeCN)]得到双核配合物[{WF4(MeCN)}2{μ-1,4- nc6h4n}] （6(MeCN)）。溶剂配体很容易被取代，如1（MeCN）、4（MeCN）和5（MeCN）与吡啶（py）或1（MeCN）与二苯甲酮（PhCOPh）反应得到1（py）、4（py）、5（py）和1（PhCOPh）。此外，1（MeCN）和2（MeCN）与[NMe4]F和NEt3·3HF反应生成钨酸盐（VI）亚胺五氟盐[cat][W（NR)F5] (R = Tol, a； DMP; b; cat = nme4,7; NEt3H, 8) 7a-8b）。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.