Metal-arene complexes tungsten

Some examples have been reported of tethered r 6-arene complexes of molyb-denum(II) and tungsten(II) that incorporate oxygen as the auxiliary donor atom.37 40 Reaction of neat 2,6-diphenylphenol with [MH4(PMePh2)4] (M = Mo, W) at 150 °C gives the tethered hydrido(aryloxo)metal(II) complexes 30 and 31.36 A metal-hydride bond is probably first cleaved by the phenolic oxygen with loss of H2 coordination of the pendant arene then induces loss of another equivalent of H2. 

A variety of transition metals, for example, chromium, molybdenum, tungsten, iron, vanadium, manganese, and rhodium can be used to prepare relatively stable j -arene complexes (see Arene Complexes). Reactions of j -arene chromium tricarbonyl complexes have been extensively examined, and numerous reviews are available. Although chromium complexes are by far the most utilized in organic synthesis, complexes of iron and manganese are emerging as potentially useful alternatives. 

Radius, U. Attner. J. Dinuclear molybdenum(III) and tungsten(III) calix[4]arene complexes — Metal-metal triple 27. bonds supported by bridging calix[4]arene ligands. Eur. J. 

Group 6 metal (chromium, molybdenum, tungsten) carbonyls trapped in zeolites have been found to undergo partial thermal decomposition to produce M(CO)3 species which react with phosphines, polyolefins, and arenes to form the expected complexes, e.g. ( / -C6H6)Cr(CO)3 [210]. 

Arene complexes are usually prepared by the displacement of more weakly bound, monodentate ligands, by oxidation or evolution of CO ligands, or by reducing a metal from a higher oxidation state in the presence of an arene. These methods have been reviewed. - In some cases, one arene will displace another. For example, hexamethylbenzene replaces p-diisopropyl benzene in the tungsten complex of Equation 2.13. This reaction is imdoubt-edly controlled by steric effects. The mechanisms of these arene exchange reactions have been clarified by Traylor and are discussed in Section 4.55. 

T -Arene complexes containing late metals have been known for many years, but the scope and utility of these complexes have increased in recent years. Copper(I) and silver form labile arene complexes of various stoichiometries that are apparently T -arene complexes. A few of these complexes have been structurally characterized. More recently, a large number of V-arene and heteroarene complexes of osmium, rhenium, molybdenum, and tungsten have been prepared for the purpose of dearomatization of the arene or heteroarenes. Two examples are shown in Figure 2.33. This dearomatization creates a diene or vinyl unit that imdergoes the organic chemistry of ttiese isolated units, instead of the chemistry of an arene. n -Arene complexes of rhodium and platinum have been characterized structurally and studied in the context of their likely intermediacy in the oxidative addition of arene C-H bonds. ... 

Chromium, Molybdenum and Tungsten.- The use of metal vapour syntheses continues to dominate the reports of new arene complexes including new complexes of Cr, W and Re with benzene and... 

Many arene metal tricarbonyl complexes where the metal is chromium, molybdenum or tungsten have been prepared by this route although the... 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

Section VII describes Cp and related V-ligand halocarbonyl complexes, and Section VIII is concerned with the little-studied Tj6-arene halocarbonyl complexes. Finally, Section IX briefly discusses the halocarbonyl complexes of molybdenum(II) and tungsten(II) containing V-cycloheptatrienyl as a ligand. As Green and Ng9 have reviewed cycloheptatrienyl and -enyl complexes of the early transition metals, only one reference in this area is given. 

There are several classic examples of the use of FTIR spectroelectrochemistry in elucidating the EC reactions of oxidized carbonyl complexes. These include the isomerization of 17e complexes for example, the isomerization of m-[Mo(CO)2(P-P)2]+ to the trans-isomer.139 Similarly, the cis-isomer of [Re(CO)2(P P)2]+ or [Re(CO)(P—P)2X] will isomerize on oxidation as monitored in a reflection IR cell.140 One-electron oxidation of [IrH(CO)(PPh3)3] is reversible, but further oxidation to the dication induces hydride oxidation and the appearance of bands due to the 16e complex [Ir(CO)(PPh3)3]+.141 Oxidation of arene tricarbonyls of Group 6 metals is frequently irreversible, especially in coordinating solvents at ambient temperature. However, the mesitylene tungsten tricarbonyl complex is oxidized by two electrons with the reversible take up of MeCN.142... 

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