Carbenes, nucleophilic

In practice, donor substituents make it possible actually to isolate a range of carbenes 4.105. With somewhat less stabilisation, the carbene 4.106, although it is only found as a reactive intermediate, is exceptionally easy to form. It is the key intermediate in all the metabolic steps catalysed by thiamine coenzymes, and its reactions are characterised by its nucleophilicity. Similarly, dimethoxycarbene 4.107 reacts as a nucleophile with electrophiles like dimethyl maleate to give the intermediate 4.108, and hence the cyclopropane 4.109, but it does not insert into unactivated alkenes. 

The carbene 4.211 is a revealing case. In spite of having a neighbouring lone pair, it is only mildly nucleophilic in character, and, unlike strongly nucleophilic carbenes, it inserts into cis- and fraw.v-2-butcncs stereospecifically.432 This carbene has the lone pair and the empty orbital held more or less orthogonal, so that the orbital overlap which stabilises the carbene 4.202 is no longer possible. 

---

The triazole 76, which is more accurately portrayed as the nucleophilic carbene structure 76a, acts as a formyl anion equivalent by reaction with alkyl halides and subsequent reductive cleavage to give aldehydes as shown (75TL1889). The benzoin reaction may be considered as resulting in the net addition of a benzoyl anion to a benzaldehyde, and the chiral triazolium salt 77 has been reported to be an efficient asymmetric catalyst for this, giving the products (/ )-ArCH(OH)COAr, in up to 86% e.e. (96HCA1217). In the closely related intramolecular Stetter reaction e.e.s of up to 74% were obtained (96HCA1899). 

The preparative value of this compound lies in the surprising fact that bis(l,3-diphenylimidazolidinylidenc-2) behaves in many reactions ie.g., with aromatic aldehydes,2,7 and with carbon acids 2 7-fJ) as if it dissociated to form a nucleophilic carbene. The hydrolytic cleavage of these derived imidazolidine derivatives makes possible the preparation of formyl compounds, so that the amino olefin can be considered as a potential carbonyla-tion reagent. In many reactions it is not necessary to isolate... 

Schrock-type carbenes are nucleophilic alkylidene complexes formed by coordination of strong donor ligands such as alkyl or cyclopentadienyl with no 7T-acceptor ligand to metals in high oxidation states. The nucleophilic carbene complexes show Wittig s ylide-type reactivity and it has been discussed whether the structures may be considered as ylides. A tantalum Schrock-type carbene complex was synthesized by deprotonation of a metal alkyl group [38] (Scheme 7). 

Jafarpour, Laleh, and Nolan, Steven R, Transition-Metal Systems Bearing a Nucleophilic Carbene Ancillary Ligand from... 

The pre.sent account follows a Journey in this arena from solution calorimetric studies dealing with nucleophilic carbene ligands in an organometallic system to the use of these thermodynamic data in predicting the feasibility of exchange reactions to applications in homogeneous catalysis. 

The versatile starting material lCp RuCI 4 (1) reacts rapidly with sterically demanding phosphines (PCy and P Pr ) as well as with the nucleophilic carbene ligands (L) to give deep blue, coordinatively unsaturated Cp Ru(L)CI complexes 2-8 (L= l,.Tbis(2,4,6-lrimethylphenyl) (IMes. 2) 1,3-R2-imidazol-2-ylidene = cyclohcxyl (ICy, 3) 4-methylphenyl (ITol, 4) 4-chlorophenyl (IPCl, 5) adamanlyl (lAd, 6) 4..5-dichloro-1,3-bis(2.4,6-trimethylphenyl) (IMesCI, 7) and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidenc (IPr. 8) in high yields according to Eq. (4). 

Ru—C(carbene) bond distances are shorter than Ru—P bond lengths, but this can simply be explained by the difference in covalent radii between P and The variation of Ru—C(carbene) bond distances among ruthenium carbene complexes illustrates that nucleophilic carbene ligands are better donors when alkyl, instead of aryl, groups are present, with the exception of 6. This anomaly can be explained on the basis of large steric demands of the adamantyl groups on the imidazole framework which hinder the carbene lone pair overlap with metal orbitals. Comparison of the Ru—C(carbene) bond distances among the aryl-substituted carbenes show... 

APPLICATIONS OF NUCLEOPHILIC CARBENES AS CATALYST PRECURSORS IN HOMOGENEOUS CATALYSIS... 

Investigating thermal stabilities of compounds 23-28 revealed that when heated to 80 C the compounds containing PPh,i i.e., 23,25, and 27, were less stable than their PCyy bearing analogues (24, 26, and 28, respectively). The least stable was (PPhy)2Cl2Ru(3-phenylindenylid-l-ene) (23) which decomposed after 2 h at 80 C (Table IX, entry 1) and the most stable was (lPr)(PPhy)Cl2Ru(3-phenylindenylid-1 -ene) (27) (Table IX, entry 4) which showed decomposition after 42 h at the same temperature. It can be concluded that the presence of the nucleophilic carbene... 

This Journey started where most of our studies are initiated from our interest in fundamental thermodynamic properties quantified by solution ealorimetry. From these data it became clear that nucleophilic carbenes (most of them anyway) are... 

---