Pseudo-organometallics

Like the amide derivatives (see Sect. 6), rare-earth metal alkoxide (aryl-oxide) complexes Ln(()R)x are pseudo-organometallics exhibiting a Ln-... 

Macroscale metal vapor reactions with alkanes have led to complex pseudo-organometallic composites, where surface H, alkyl, C, CH, CHj, etc. are bound to metal cluster surfaces Thus, C-H and C-C cleavage occurs on metal atoms or metal clusters in the matrix as it warms. For Ni only clusters react in this way, whereas for Zr, atoms and clusters react ... 

Formation of ketones. Ketones can be prepared by the carbonylation of halides and pseudo-halides in the presence of various organometallic compounds of Zn, B, Al, Sn, Si, and Hg, and other carbon nucleophiles, which attack acylpalladium intermediates (transmetallation and reductive elimination). 

Examples in organometallic systems are known. Reaction of thiuram disulfides, (R2NCS2)2, with Co(Cp)(CO)2 produces dithiocarbamato pseudo-octahedral cobalt(III) complexes Co(Cp)(dtc)2 with one chelated and one monodentate dtc, also accessible via Co(Cp)I(dtc).1050 Fluxional behavior, including monodentate chelate exchange, was observed for some complexes in temperature-dependent NMR studies. The Co(Cp)I(dtc) complex was defined in a crystal structure. 

The two chemically different zinc atoms show decidedly different coordination environments. Thus, the inorganic zinc atom (Znl) has an octahedral environment and is surrounded by four oxygen and two nitrogen atoms, while the organometallic zinc atom (Zn2) is in the pseudo-tetrahedral environment of one ethyl group and three oxygen atoms. 

Organometallic Alkyls, Aryls, Hydrides, and (Pseudo)Halides 288... 

Syntheses and Structures of Organometallic (Pseudo)Halides RxMX3, x (X = Halogen, N3) 294... 

The rate of reaction of propylene over the MeReOs/HMDS/silica-alumina catalyst (1.4 wt% Re) is shown in Figure 2b. The profile is similar to that of the Sn-promoted perrhenate catalyst, with kobs = (1-78 + 0.09) x 10" s, and the activity responds similarly to subsequent additions of propylene. In fact, the pseudo-first-order rate constant for the organometallic catalyst lies on the same line as the rate constants for the Sn-promoted perrhenate catalyst. Figure 3. Therefore we infer that the same active site is generated in both organometallic and promoted inorganic catalyst systems. 

Enantiomers of so-called pseudo-asymmetric organometallic compounds (20)-(22), in which a coordination site on a tetrahedron or square pyramid is occupied by an 775 - cyclopentadienyl or i76-arene ring (or similar 71-donor ligands), have been well characterized however, due largely to the efforts of Brunner and coworkers.150,151... 

Fig. 58. Portion of the pseudo-two-dimensional extended structure of [K(/i-ij5,ij5-C5H5)2 Nd(OC6H3Me2-2,6)2], 95. (Reprinted with permission from W. J. Evans et al., Organometallics 1995, 14, 558. Copyright 1995 American Chemical Society.)...

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