Metal carbonyls electron counting

Ligands Bonding and spectroscopy 18-electron rule Metal carbonyls Isolobal principle Electron counting schemes Types of organometallic reactions... 

The foregoing examples show the relevance to metal-carbonyl cluster chemistry of the borane-oarborane structural and bonding pattern. Its relevance to other areas of chemistry may be explored readily using a systematic skeletal electron-counting procedure (161, 201). 

The highly covalent nature of transition metal carbonyls and their derivatives leads to the 18-electron rule being closely followed. The mononuclear species Ni(CO)4, Fe(CO)5, Ru(CO)5, Os(CO)5, Cr(CO)6, Mo(CO)6 and W(CO)6 obey this well and, if the formalized rules of electron counting are applied, so do the metal—metal bonded and carbonyl bridged species. Such compounds are therefore coordinately saturated and the normal (but by no means unique) mode of substitution is dissociative (a 16-electron valence shell being less difficult to achieve than one with 20 electrons).94... 

One aspect of metal carbonyl chemistry that should be mentioned in surveying the more commonly found modes of CO coordination is the stereochemical nonrigidity of carbonyl clusters. This aspect has received considerable attention over the past decade, especially as 13C nmr instrumentation has become more readily available. In many carbonyl clusters, terminal and bridging carbonyls as established by x-ray structural studies are equilibrated on the nmr time scale (37, 39-41). The manner of equilibration takes place in a concerted way in order that each metal center maintains a constant electron count. For example, bridge terminal interconversion, (1), proceeds via complementary unsymmetrical CO bridges. 

The electron counting rules of Wade (S3), Williams (117), and Rudolph (118) can serve as a useful concept to explain structure and bonding in a variety of systems which at first glance are very different Zintl phases, boranes and carboranes, transition metal n complexes and carbonyl clusters, nonclassical carbocations, and also n complexes of main-group elements. According to... 

Nearby elements also display chemistry reflecting alkyne 7rx donation to a vacant metal dir orbital. In Group V, Lippard s coupled carbonyl product Ta(Me3SiOC=COSiMe3)(dmpe)2Cl is a d4 Ta(I) alkyne monomer (116), similar in electron count to CpV(CO)2(RC=CR) complexes (231). The preparative route and physical properties of a series of Ta(CO)2-(RC=CR)(I)L2 d4 monomers are compatible with a four-electron donor description for the alkyne ligands (231a). The d2 configuration has also... 

The nitrosonium cation [NO]+ is isoelectronic with CO and accordingly many mixed nitrosyl-carbonyl complexes are known. For electron counting purposes, the neutral molecule is considered to act as a 3 (or occasionally 1) VE donor. Thus various series of isoelectronic complexes can be envisaged (Table 3.5). The majority of synthetic routes to nitrosyl-carbonyl complexes involve (i) photochemical CO substitution or metal-metal bond cleavage by NO (ii) electrophilic attack by nitrosonium salts, e.g. [NO]BF4 or nitrosyl halides (e.g. C1NO) upon electron-... 

Carbyne ligands may bridge two (p) or three (p3) metal centres, providing a total of 3VE to the overall electron count. Earlier synthetic routes to such complexes involved the reactions of carbonyl metallates with 1,1,1-trihaloalkanes, or the cleavage of alkyne ligands coordinated to clusters (Figure 5.46). 

Group 10 metal clusters with carbonyl and phosphine ligands sometimes fail to follow the counting paradigm, but the reason for this failure differs from those discussed up to now. The situation is illustrated by the two Pt carbonyl clusters shown in Figure 3.21 where the eve counts are four less than those obtained for group 8/9 metal clusters for the same cluster shapes. What is the origin of these lower electron counts ... 

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