15-electron species

Similar differences are found for organic azides (e.g. MeN3). In ionic azides (p. 417) the N3 ion is both linear and symmetrical (both N-N distances being 116 pm) as befits a 16-electron species isoelectronic with CO2 (cf. also the cyanamide ion NCN, the cyanate ion NCO, the fulminate ion CNO and the nitronium ion N02 ). 

These are diamagnetic 16 electron species (reaction in methanol or 2-meth-oxyethanol gives OsH(CO)Cl(PR3)2, presumably because the alcohol is oxidized to an aldehyde that can be a source of CO) (Figure 1.65). These... 

Counting NO as a three-electron donor, [IrCl(NO)(PPh3)2]+ is, therefore, a 16-electron species isoelectronic with Vaska s compound, isolable as a red crystalline hexafluorophosphate (m.p. 211°C, i/(N-0) 1870 cm-1) or similar perchlorate and tetrafluoroborate a trans-structure is indicated by spectroscopic data, and it is presumed to have a linear Ir-N-0 grouping. 

More recently, Grubbs et al. obtained a refined mechanistic picture of the initiating step by conducting a 31P NMR spectroscopic study of the phosphine exchange in precatalysts 12-A. These investigations revealed that substitution of the phosphine proceeds via a dissociative-associative mechanism, i.e., a 14-electron species 12-B is involved that coordinates the alkene to give a 16-electron species 12-C (Scheme 12) [26a]. Increased initiation rates are observed if the substituents R and the phosphine ligands PR3 in precatalysts... 

The formation of the complexes shown in Scheme 14 and Eq. (5) has been rationalized according to Scheme 15. Thus, it has been proposed that the insertion of the Os—H bond of OsHCl(CO)(P Pr3)2 into the carbon-carbon triple bond of the alkynol initially gives five-coordinate (E )-alkenyl intermediates, which subsequently isomerize into the Os CH=CHC(OH)R1R2 derivatives. The key to this isomerization is probably the fact that the five-coordinated ( )-alkenyl intermediates are 16-electron species, while the Os CH=CHC(OH)R1R2 derivatives are... 

A possible formulation for I is illustrated below. This could be formed by the heterolytic cleavage of a Ru-Ru bond an corresponding movement of a carbonyl from a terminal site to a bridging one to maintain the charge neutrality of both Ru atoms. The result would be to leave one ruthenium atom electron deficient (a 16 electron species) and capable of coordinating a two electron donor to give another intermediate I. ... 

This species adds a ketone yielding the alkoxide complex (84) which, after reductive elimination of the corresponding alcohol, generates the 16-electron species (85). This intermediate undergoes oxidative addition of 2-propanol (species (86)) and subsequent reductive elimination of acetone, regenerating the hydride complex (83). 

Figure 22.13 shows the scheme used to describe the hydroformylation process. The active catalyst is HCo(CO)3, which is a 16-electron species that is coordinatively unsaturated. After that species is generated, the first step of the catalyzed process involves the addition of the alkene to the catalyst. In the next step, an insertion reaction occurs in which the alkene is inserted in the Co-H bond (nucleophilic attack by H on the alkene would accomplish the same result as described... 

Check of the electron deficiency of catalytically active species (10- to 16-electron species)... 

A large number of transition metal complexes whose cationic complexes are 10- to 16-electron species (including those with the ligands summarized in Fig. 7) were investigated to determine their potential as ethylene polymerization catalysts with methyaluminoxane (MAO) activation at 25 °C under atmospheric pressure. As a result, we discovered a number of high-activity catalysts for ethylene polymerization that contain electronically flexible ligands [11]. 

The catalysts are best prepared in situ by mixing a half-equivalent of the di-chloro-metal aromatic dimer with an equivalent of the ligand in a suitable solvent such as acetonitrile, dichloromethane or isopropanol. A base is used to remove the hydrochloric acid formed (Fig. 35.3). If 1 equiv. of base is used, the inactive pre-catalyst is prepared, and further addition of base activates the catalyst to the 16-electron species. In the IPA system the base is conveniently aqueous sodium hydroxide or sodium isopropoxide in isopropanol, whereas in the TEAF system, triethylamine activates the catalyst. In practice, since the amount of catalyst is tiny, any residual acid in the solvent can neutralize the added base, so a small excess is often used. To prevent the active 16-electron species sitting around, the catalyst is often activated in the presence of the hydrogen donor. The amount of catalyst required for a transformation depends on the desired reaction rate. Typically, it is desirable to achieve complete conversion of the substrate within several hours, and to this extent the catalyst is often used at 0.1 mol.% (with SCR 1000 1). Some substrate-catalyst combinations are less active, requiring more catalyst (e.g., up to 1 mol.% SCR 100 1), in other reactions catalyst TONs of 10000 (SCR 10000 1) have been realized. 

The hydrido-cobalt-tetracarbonyl complex (I) undergoes a CO-dissocia-tion reaction to form the 16-electron species HCo(CO)3 (II). This structure forms a 7r-complex (III) with the substrate and is a possible explanation for the formation of further (C = C)-double bond isomers of the substrate. In the... 

In the next step of the reaction cycle, the carbon monoxide is inserted into the carbon-cobalt bond. At this time, the subsequent aldehyde can be considered as preformed. This step leads to the 16 electron species (VI). Once again, carbon monoxide is associated to end up in the 18 electron species (VII). In the last step of the reaction cycle, hydrogen is added to release the catalyti-cally active hydrido-cobalt-tetracarbonyl complex (I). Likewise, the aldehyde is formed by a final reductive elimination step. 

It is also called dissociative because one of the rate-determining steps is the dissociation of carbon monoxide. The cycle is started by the dissociation of a ligand, which results in the release of the planar 16 electron species (I). In analogy to the cobalt mechanism (see Wiese KD and Obst D, 2006, in this volume), the next step is the addition of an olefin molecule to form the r-complex (II). This complex undergoes a rearrangement reaction to the corresponding reaction steps decide whether a branched or a linear aldehyde is the product of the hydroformylation experiment. The next step is the addition of a carbon monoxide molecule to the 18 electron species (IV). Now, the insertion of carbon monoxide takes place and... 

Complex exo-60 is then protonated to give the 773-vinylcarbene complex exo-64, which subsequently inserts carbon monoxide in the well-established manner (see Sections II,B, V,B, VI,B, VI,C, VI,E, VI,J, and VII), affording the 16-electron species endo-65. Anion trapping of the unsaturated species finally yields the vinylketene complex endo-62. 

A catalytic example of C-S bond breakage in benzothiophene has been reported by Bianchini [47], A catalytic desulfurisation was not yet achieved at the time as this is thermodynamically not feasible at such mild temperatures because of the relative stability of metal sulfides formed. Bianchini used a water-soluble catalyst in a two-phase system of heptane-methanol/water mixtures in which the product 2-ethylthiophenol is extracted into the basic aqueous layer containing NaOH. Figure 2.43 gives the reaction scheme and the catalyst. The 16-electron species Na(sulfos)RhH is suggested to be the catalyst. Note that a hydrodesulfurisation has not yet been achieved in this reaction because a thiol is the product. Under more forcing conditions the formation of H2S has been observed for various systems. 

According to Wade s rules, one non-bonding electron pair is allocated to each metal atom in polyionic metal clusters of the p-block elements. Thus the planar five-membered M5 anions are 16-electron species comprised of two valence electrons contributed by each metal atom and the 6- charge. Since there are eight electron pairs for bonding five cluster atoms, Wade s rules predict an arachno structure ( + 3 electron pairs for n cluster atoms), i.e. a pentagonal bipyramid with two vacant sites. 

Gold(III) has a d8 electronic configuration, and its complexes are usually four coordinate. These 16-electron species are square planar, and hence diamagnetic, and are quite amenable to study by NMR techniques. 

This is very common especially for dt species. A 16-electron species may add H2 directly, but an 18-electron species must lose a ligand first. A concerted H2 homolysis is often invoked, perhaps from... 

The 16-electron species invariably must be stabilized by addition of an external ligand or by internal coordination. For example, as will be discussed later, acylation of a [Fe(diene)(CO)3] complex yields a... 

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