Cyclopentadienyl complexes bonding

Beryllium forms a series of cyclopentadienyl complexes [Beftj -CsHiY] with Y = H, Cl, Br, Me, —C=CH and BH4, all of which show the expected C5, symmetry (Fig. 5.10a). If the pe/ifo/topfo-cyclopentadienyl group (p. 937) contributes 5 electrons to the bonding, then these are all 8-electron Be complexes consistent with the octet rule for elements of the first short... 

Nucleophiles, at the exocyclic methylene when bonded to Ir, Rh, and Co cyclopentadienyl complexes.17... 

Despite a common perception that organometallic chemistry essentially belongs in the province of catalysis rather than in vivo applications because of high reactivity of metal carbon bonds, certain organometallic species have very high kinetic stability. Indeed, this point is highlighted by the present wide application of the isonitrile complex Tc(ses-tamibi), [Tc(2-methoxyisobutylisonitrile)6]+, in myocardial imaging. Rhenium tricarbonyl and cyclopentadienyl complexes offer further ex-... 

Insertions of isocyanide into niobium-carbon bonds follow a path similar to that with vanadium, resulting in the formation of the 7]2-iminoacyl complexes, which can then be involved in further chemistry.175 176 The reaction of acetone with cyclopentadienyl complex 110 under a carbon monoxide atmosphere gives the if -acetone compound 111. Complex 111 subsequently undergoes either stepwise insertion of two isocyanides via 112 or double insertion of the isocyanide to give complex 113 (Scheme 48).177... 

A stabilized heteroleptic germanium cyclopentadienyl complex was obtained which has an extremely long (2.369(1) A) Ge-Cl bond and an 2-bound Cp ring (Equation (238)).309... 

One other structure of a tricyclopentadienide has appeared (57) and it provides a further demonstration of the correlation between ionic size and coordination. Neodymium tris(methylcyclopentadienide) crystallizes as a tetramer (Fig. 10). The Nd + ion (which is slightly larger than Sm3+) is pentahapto bound to three cyclopentadienyl rings and monohapto bound to a fourth ring. This fourth ring is in turn j -bonded to another Nd + ion, until the tetramer is generated. The distances between tetramers are those expected for van der Waals contact. The crystal and molecular parameters are compared with the other tris cyclopentadienyl complexes in Table 5. 

The Lu—C sigma bond is about 0.2 A shorter than the pentahapto coordinated Sm—C bond in tris-cyclopentadienyl complex (Sm—C =2.76 A) taking account of the difference of ionic radii of 0.11 A between Sm and Lu (Table 1). 

According to the general idea presented by Wolczanski [4], alkoxide and siloxide (alternative to cyclopentadienyl complexes) of transition metals are bonded through a o-type orbital such as the sp hybrid and via Jt-donation of two pjt orbitals perpendicular to the M-O direction (Figure 7.1). 

The tetramethylethanediyl-bridged, f-butyl-substituted bis-cyclopentadienyl complex Me4C2(3-f-BuC5H3)2Mg(THF) (129) is present in the solid state as a me o-diastere-oisomer. It has a structure in which both cyclopentadienyl groups are /7 -bonded to magnesium while only one THF molecule is coordinated to magnesium (Figure 62) . 

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. 

Organosilyl substituted 7)5-cyclopentadienyl complexes may be prepared by two main procedures (a) reactions of silylated cyclopenta-dienes or their alkali metal derivatives, with an appropriate transition metal compound (carbonyl or halide) with formation of ir-bonds (b) metalation of a preformed 7j5-cyclopentadienyl complex, followed by treatment with an organohalosilane. 

A very versatile preparation seems to be the elimination of organotin halides in the reaction of organostannyl-organosilylcyclopentadienes with metal carbonyl halides. This reaction is very selective and only Sn—C bonds are cleaved with formation of 7)5-cyclopentadienyl complexes (7) ... 

G. Cyclopentadienyl Complexes and Aryl Complexes Containing 3-Center 2-Electron Bonds... 

The types of compounds formed by gold(I) and gold(III) often differ from those of other metals due to the constraints imposed by coordination number and electron count at the metal. Thus, for example, whereas 7r-bonded cyclopentadienyl complexes of palladium and platinum are numerous (336), and a copper(I) species of this type is known (337), cyclopentadienyl complexes of univalent (94, 96, 97) and trivalent (228) gold have invariably been found to be fluxional behavior, similar to that in dicyclopentadienylmercury, was involved (228). 

X-ray analysis of complex 9 shows two independent molecules in the unit cell. The Hf—Si bonds of 2.881(4) A and 2.888(4) A are longer than those found in other d° Zr—Si derivatives (Table 1), reflecting the steric hindrance in 9. The crystal structure of the mixed cyclopentadienyl complex CpCp Hf(SiH2Ph)Cl reveals a Hf—Si bond length of 2.729(3) A, which is shorter than in 9, presumably due to a lower steric interaction... 

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