Diynyl complexes, preparative methods

The chemical reactivity of the C=CH portion of terminal 1,3-diynyl ligands is often found to resemble that of conventional organic 1-alkynes.36 Consequently, numerous examples of heterometallic diyndiyl complexes have been prepared (Table VI). The most frequently used methods involve metallation of terminal diynyl complexes MLX C=CC=CH, usually with similar synthetic protocols to those described for the preparation of diynyl and homometallic diyndiyls. General methods include ... 

RDienyl)Fp (17) is known for a limited number of substitution patterns, normally being prepared by the FpNa (5) + dienyl chloride route. (jjNCyclopentadienyOFp complex (18a) has been prepared by the reaction of NaCp with Cp(CO)2FeI (6c). Substituted versions of these complexes can also be made by this method (compounds 18b,c and 19) or in the case of (20) by reaction of Cp Fe(CO)2+Bp4 with the cyclopentadiene, followed by triethylamine-induced proton abstraction of the intermediate alkene complex (19,20). It is also possible to replace one CO ligand of (18) by carefully selected phosphite ligands by the photolysis method used for ()]Callyl)Fp complexes. (jj -Diynyl)Fp (21) has been prepared as well. ... 

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