Carbyne cycloadditions

Metallacyclopent-l-enes have been obtained by formal [2 + 3] cycloaddition of ethylene to Re(CtBu)(CHtBu)(OR)2 (a carbene/carbyne complex) [612]. Nucleophilic tungsten(II) complexes can react directly with cyclopentanone to yield cyclopentylidene complexes [613]. 

Fig. 3.30. Preparation of carbene complexes by sequential [2 + 2] cycloadditions and [2 + 2] cycloreversions of carbene and carbyne complexes to alkenes and alkynes [596-598].

A closely related formation of >/3-cydopropenyl molybdenum complex Cp P(OMe)3)2Mo( 3-C3Ph2Me), possibly involving an interamolecular ligand cycloaddition within a carbyne-acetylene intermediate complex, has been accomplished by treating the acetylenic cation complex [Cp f P(OMe)3 2Mo( 2-PhC=CPh)]BF4 with vinylmagne-sium bromide in THF (equation 253)321. 

Metal carbonyl monoanions, with trivalent Group 13 element halides, 3, 347, 3, 357 Metal carbynes, Fe-containing, 6, 325 Metal-catalyzed cycloadditions, alkenyl- and alkynylboron compounds, 9, 180 Metal cation receptors characteristics, 12, 466 ferrocene-based, 12, 466 Pt- and Au-based receptors, 12, 471 types, 12, 473 Metal chalcogenides... 

The reversible [2+2] cycloaddition of metal alkylidyne or Fischer-type metal carbyne complexes remains the only general methodology for the synthesis of metallacyclobutadiene complexes. Recent literature revolves principally around the heavier group 6 metals and the investigation of intermediates in catalytic alkyne metathesis (Scheme 25 Equation 45) <1996CHEC-II(lb)887> (W <2005OM4684>, Mo <2003JOM56>). 

A recent computational investigation of the [2+2] cycloaddition between a hypothetical molybdenum carbyne complex, CbMo CI I, and ethyne suggests that the formation of the molybdacyclobutadiene, CI3Mo(7/2-C3l l (), is allowed by orbital symmetry. In contrast, the direct formation of the isomeric molybdatetrahedrane (i.e., the if -cyclopropene complex), ChMoft -CsID, is symmetry forbidden <19930M1289> such complexes presumably arise by isomerization subsequent to initial molybdacyclobutadiene formation (Section 2.12.5). 

Molybdenum and tungsten carbyne (alkylidyne) complexes frequently undergo 2+2 cycloaddition reactions with alkynes to give the corresponding metallacyclobutadiene... 

Carbyne complexes containing the Mn=CR moiety undergo an interesting variety of reactions. " Scheme 13 provides a sampler of these reactions. The electrophilic nature of the carbyne in the cationic Cp(CO)2Mn=CR" has been exploited in cycloadditions, metatheses, and ketene formation methodologies. Extended chains containing unsaturated carbon networks that are truncated by metal... 

The molecular orbital analysis of the nucleophilic addition at the carbyne C atom infers the orbital control of the reaction since the C atom undergoing attack is the most negative one in the carbyne complex. [2 + 2] cycloadditions of [ReCp(CO)2(CPh)]+ with MeN=C(Ph)H, t-BuN=0, and ArN=NAr (Ar = aryl) but not with aUcenes or aUcynes, give the metallacycles. These reactions are driven by the nucleophilic attack of the lone pairs of the N atom at the electrophilic carbyne carbon atom. These metallacycles are... 

The cycloaddition of imines to the metal-carbon triple bond in the cationic rhenium carbyne complex 263 was reported by Geoffroy and... 

Transition metal carbyne complexes are described by the general formula L M=CR where the carbyne ligand (=CR) is bonded to the metal by a metal-carbon triple bond. Transition metal carbene complexes have found numerous applications in synthetic organic chemistry through a variety of carbene transfer and cycloaddition reactions [17]. In contrast, carbyne (L M=CR) and vinylidene (L M=C=CRR ) complexes have far fewer applications, in part because their overall chemistry is significantly less developed [18]. Addition reactions to transition metal vinylidene complexes will be discussed in Chapter 21. The first successful synthesis of a carbyne complex was reported by Fischer and co-workers in 1973 [Eq. (8) 19]. Subsequently, many other carbyne complexes have been synthesized by the classic route of Fischer or by new synthetic methods [20]. 

It is conceivable that a parallel bundle of linear polyyne chains (the carbon allotrope named chaoite or carbyne) may form, via thermally-allowed (4 + 2)-n-electron cycloadditions, six-membered rings which lead to graphene sheets and/or nanotubes. However, the mechanism of nanotube formation in a plasma produced by arc discharge appears to require the presence of a transition metal atom at the rim of the growing nanotube [77 j. 

By analogy to olefin metathesis, alkyne metathesis occurs between a complex containing a metal-carbon triple bond - a metal carbyne (or alkylidyne) - and an alkyne substrate [66]. As illustrated in Fig. 4.21, this mechanism parallels the Chauvin mechanism for olefin metathesis after alkyne coordination to the metal center, [2 - - 2] cycloaddition between the metal carbyne and the alkyne yields a metallacyclobutadiene, which rearranges and fragments productively to afford a new carbyne and a new alkyne (Fig. 4.21) [54]. 

A proposed mechanism for ROMP reactions with this carbyne complex starts with the [2+2] cycloaddition of the olefin to the W=C triple bond. 

Heterogeneous, bimetallic metathesis catalysts are formed by reactions of Fischer type carbyne tungsten or molybdenum complexes with the reduced Phillips catalyst, a suface chromium(II) compound on silica (14).(scheme 5). The bimetallic surface compounds can result from 2+1 cycloaddition reactions. Similar reactions are well known by the work of Stone (15). 

Cationic carbyne complexes within the [Cp(CO)2MsCR] (M = Mn, Re) family were shown by the early studies of E. O. Fischer and co-workers to be highly electrophilic at the carbyne carbon and to add a variety of nucleophiles to yield carbene derivatives [1]. As illustrated in Scheme I, we recently reported that new cycloaddition reactions of... 

As illustrated in eqs. 1 and 2, azobenzene, azotoluene, and benzo[c]cinnoline have been found to undergo net [2+2] cycloaddition of their N=N double bond across the R C triple bond of the BPh4 salt of carbyne complex 1 [3]. These reactions represent the... 

The reaction of dicarbonyl(t 5-cyclopentadienyl)-carbyne complexes Cp(CO)2-n(PMe3)nMsC-R (M = Mo, W n = 0, 1 R = Me, Ph, Tol) with azides, N3R (R = CO2CH3, CH2CO2CH3), results in a [3+2]-cycloaddition to the electron rich metal carbon triple bond, leading to neutral 1-metalla-2,3,4-triazole complexes in high yields [43,44]. 

Carbon dioxide reacts with an anionic carbyne compound to furnish a cycloaddition product. 

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