Cyclopentadiene, reactions with metal

Several preparations of silylated cyclopentadienylmetal complexes involve the formation of a triorganosilylcyclopentadienyl anion (by treatment of a silylated cyclopentadiene with an alkali metal in tetrahy-drofuran or by metalation with n-butyllithium), followed by reaction with metal chlorides. This type of reaction has been used for the synthesis of silylated ferrocenes (41, 43, 58, 83, 84, 103, 107, 116, 135, 142, 171, 172), cobaltocenes (135), nickelocene (135), titanium cyclopen-tadienyls (46, 145), and cyclopentadienylmanganese tricarbonyl (30) [Eqs. (19) and (20)]. It is remarkable that Si—C5H6 bonds are not... 

Zirconium and hafnium dialkylamides are highly reactive compounds. They undergo (i) protolytic substitution reactions with reagents such as alcohols, cyclopentadiene and bisftrimethylsilyOamine 63 64 (ii) insertion reactions with C02, CS2, COS, nitriles, phenyl isocyanate, methyl isothiocyanate, carbodiimides and dimethyl acetylenedicarboxylate 69-72 and (iii) addition reactions with metal carbonyls.73 These reactions are summarized with reference to Zr(NMe2)4 in Scheme 1. 

Reaction of cyclopentadiene directly with metal chips under reflux or in liquid ammonia has been used in the preparation of the M(C5H5)291-92 and Ca(C5H4Me)2(DME)93 compounds, respectively. However, a more general reaction method is co-condensation of metal vapor, the vapor of the cyclopentadiene of choice, and the solvent, which is typically hexane or toluene, according to Eq. (1 1).88-89,94... 

During reactions with metal carbonyls, cyclopentadiene complexes are probably first formed which subsequently undergo rearrangement to hydridocyclopentadienyl compounds followed by decomposition with hydrogen evolution ... 

While this is the simplest method for preparing metal cyclopentadienyl compounds, it is one of the least general. It is limited to the elements Li, Na, K, Ca, and Sr and under rather vigorous conditions of temperature to Mg, In, Tl, and Fe. The reaction is usually carried out in the liquid phase at 25° to 100° C in the presence of a solvent for lithium, sodium, and potassium, or in the vapor phase at 400°- 600°C for the less reactive elements. Usually the cyclopentadienides of lithium, sodium, and potassium are not isolated but are used in solution as intermediates for the preparation of other cyclopentadienyl metal compounds. Compounds produced by reaction of cyclopentadiene vapor with metal are usually sufficiently volatile to sublime away from the reaction zone and condense in the cooler portion of the apparatus. 

Methylcyclopentadiene readily undergoes reaction with metal carbonyls 47) and even 1,3-diphenylcyclopentadiene reacts with iron carbonyl 4S). A novel method for obtaining a ferrocene with one substituted ring, is the reaction of 1,3-diphenylcyclopentadiene with the dimer of cyclopentadienyl-iron dicarbonyl at 170° C to produce 1,3-diphenylferrocene in 15% yield. Other substituted cyclopentadienes which have been used are tetraphenyl-cyclopentadienone in the preparation of tetraphenyl(hydroxy)cyclopenta-dienylmanganese tricarbonyl 49) and indene in the preparation of the dimer of indenylmolybdenum tricarbonyl (50). A variety of substituted fulvenes have been used in the preparation of substituted cyclopentadienyl metal tricarbonyl compounds of Cr, Mo, and W (57, 52). This latter reaction proceeds best in the presence of a solvent, such as 1,2-dimethoxyethane, to permit easy abstraction of hydrogen. 

It is believed that clay minerals promote organic reactions via an acid catalysis [2a]. They are often activated by doping with transition metals to enrich the number of Lewis-acid sites by cationic exchange [4]. Alternative radical pathways have also been proposed [5] in agreement with the observation that clay-catalyzed Diels-Alder reactions are accelerated in the presence of radical sources [6], Montmorillonite K-10 doped with Fe(III) efficiently catalyzes the Diels-Alder reaction of cyclopentadiene (1) with methyl vinyl ketone at room temperature [7] (Table 4.1). In water the diastereoselectivity is higher than in organic media in the absence of clay the cycloaddition proceeds at a much slower rate. 

To conclude, we shall mention some metal-atom reactions with boranes (172) and carboranes (173). When cobalt atoms reacted with pentaboraneO) and cyclopentadiene, a number of new metalloborane clusters were formed (172), two of which were 65115003(17-05115)3 and cyclopentyl-B5H40o2(i7-05H5)3. Possible structures for the former are shown in Fig. 42. The reaction of cyclopentadiene, pentaboraneO), and 2-butyne with cobalt atoms yielded the metallocarborane species illustrated in Fig. 43 (173). 

An alternative synthesis of a thermally stable cyclopentadienyl functionalized polymer involved ring bromination of poly(oxy-2,6-diphenyl-l,4-phenylene), followed by lithiation with butyl lithium to produce an aryllithium polymer. Arylation of 2-norbornen-7-one with the metalated polymer yielded the corresponding 2-norbornen-7-ol derivative. Conversion of the 7-ol to 7-chloro followed by treatment with butyl lithium generated the benzyl anion which undergoes a retro Diels-Alder reaction with the evolution of ethylene to produce the desired aryl cyclopentadiene polymer, 6. 

This review deals with metal-hydrocarbon complexes under the following headings (1) the nature of the metal-olefin and -acetylene bond (2) olefin complexes (3) acetylene complexes (4) rr-allylic complexes and (5) complexes in which the ligand is not the original olefin or acetylene, but a molecule produced from it during complex formation. ir-Cyclopentadienyl complexes, formed by reaction of cyclopentadiene or its derivatives with metal salts or carbonyls (78, 217), are not discussed in this review, neither are complexes derived from aromatic systems, e.g., benzene, the cyclo-pentadienyl anion, and the cycloheptatrienyl cation (74, 78, 217), and from acetylides (169, 170), which have been reviewed elsewhere. 

The interaction of metal atoms with cyclopentadiene is characterized by a tendency toward formation of a stable electronic configuration for the metal. Thus, cyclopentadiene undergoes the following reactions on condensation with metal vapors at -196°C (21, 115, 127, 136) ... 

Compounds with a narrow HOMO-LUMO gap (Figure 5.5d) are kinetically reactive and subject to dimerization (e.g., cyclopentadiene) or reaction with Lewis acids or bases. Polyenes are the dominant organic examples of this group. The difficulty in isolation of cyclobutadiene lies not with any intrinsic instability of the molecule but with the self-reactivity which arises from an extremely narrow HOMO-LUMO gap. A second class of compounds also falls in this category, coordinatively unsaturated transition metal complexes. In transition metals, the atomic n d orbital set may be partially occupied and/or nearly degenerate with the partially occupied n + 1 spn set. Such a configuration permits exceptional reactivity, even toward C—H and C—C bonds. These systems are treated separately in Chapter 13. 

Metallacyclopentadienes undergo a range of synthetically versatile reactions which proceed with extrusion of the metal atom and attendant ligands. Thus, reactions with alkenes and alkynes afford cyclohexa-1,3-dienes and arenes (Scheme 6), and thiophenes, selena-cyclopentadienes, pyrroles and cyclopentadienones (indenones, fluorenones) can be obtained by treatment with sulfur, selenium, nitroso compounds and CO, respectively. The best studied substrates for such reactions are cobaltacyclopentadienes of the type (24a), which have been converted into a wide variety of arenes, cyclohexadienes and five-membered heterocycles, many of which would be very difficult to obtain by conventional organic procedures (74TL4549, 77JOM(139)169, 80JCS(P2)1344). 

Reaction of metallic europium with cyclopentadiene in liquid ammonia yields [478] a yellow europous-dicyclopentadienyl (eq. 41) complex. Magnetic measurements on this compound (jn = 7.62 Bohr magneton) and its infrared spectrum definitely confirm the divalent state of europium. 

The reaction of metal cyclopentadienyl compounds with organosilicon electrophiles has been the most widely applied method for the synthesis of silylated cyclopentadienes (see Scheme 3) since the beginning of cyclopentadienylsilicon chemistry1. 

Caution. Diazo compounds are potentially explosive. Although neat 5-diazo-l,3-cyclopentadiene is known to be highly explosive,6 it may be handled conveniently and safely in a pentane solution.2,1 Tetrachloro-5-diazo-l,3-cyclopentadiene is reported to be stable, but due caution should be exercised in the manipulation of this compound. Carbon monoxide, volatile metal carbonyls, and some diazo compounds are highly toxic, and reactions with these species should be conducted in a well-ventilated fume hood. Avoid inhalation or contact with skin. 

The 1,4-diphospha-l,3-butadienes are suitable as ligands for cr-coordi-nated complexes with transition metals. Attempts to carry out pericy-clic reactions with maleinic anhydride, acetylene dicarboxylate esters, dimethylbutadiene, or cyclopentadiene failed, but Diels-Alder reactions with norbornadienes were successful (94). Earlier attempts to synthesize 1,4-diphosphabuta-l,3-dienes with oxalychloride and phenyl-bis(silyl)phosphane proceeded via ring closure [Eq. (42)] (89), where R = Ph (a) or [Pg.285]

The reaction of M3(CO)12 with both open-chain and cyclic poly-alkenes has attracted some attention, especially in the case of Ru3(CO)i2. In most of the examples reported, the organic fragment bonds to the metal framework in such a way as to interact with more than one of the three metal atoms (68-77). There are some exceptions to this general statement, however. One is the reaction of Ru3(CO)j 2 with cyclopentadiene, in which a mononuclear complex is obtained (78). In other cases, tetranuclear and hexanuclear compounds are obtained (79 81). Cluster breakdown has also been observed in the case of a rhodium complex upon reaction with ethylene (55) as shown in Fig. 3. 

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