Ruthenium-alkynyl complexes

Unlike the ruthenium alkynyl complex in Table III, the iron complex 328 does not undergo insertion with CS2, but forms a [2 + 2] cycloaddition product (329) containing a 2//-thiete-2-thione 08-dithiolactone) functional group, which can react further with electrophiles, for example, Mel. The CS2 addition was found to be reversible in solution and in the solid... 

We have also studied a further ruthenium-containing series of complexes with a different ligand set, namely chlorobis(bidentate phosphine)ruthenium alkynyl complexes, the results from which are summarized in Table 4, and efficient examples illustrated in Figure 8. 

The dendritic ruthenium alkynyl complexes have very large cubic NLO coefficients. Inspection of y values for trazi -[Ru(C=CCgH4-4-C=CPh(C=CPh) (dppe)2] and [1, 3, 5-CgH3-trans - C=C-4-C=CCgH4C=C[Ru(C=CPh)(dppe)2] 3]... 

Figure 1.8 Selected cyclopentadienyl ruthenium alkynyl complexes...

For the metal—alkyne fragmait, nonlinearity also increases upon increasing valence electron count [14 valence electron (triphenylphosphine) gold alkynyl compounds <18 valence electron (cyclopentadienyl) (triphenylphosphine)nickel, and (cyclopentadienyl) bis(triphenylphosphine) ruthenium alkynyl compounds] and increasing ease of oxidation (less easily oxidizable (cyclopentadienyl)(tri-phenylphosphine)nickel alkynyl complexes < more easily oxidizable (cyclopen-tadienyl)bis(triphenylphosphine)ruthenium alkynyl complexes). 

Switching the cubic nonlinearity of ruthenium alkynyl complexes by a protmi-ation/deprotonation sequence (via a vinylidene complex) was demraistrated by fs Z-scan studies at 800 nm several years ago [41]. Recently, protic and electrochemical switching were demonstrated in the ruthenium alkynyl cruciform complex 11 for which distinct linear optical and NLO behavior were noted for the vinylidene complex and the Ru(II) and Ru(III) alkynyl complexes [42]. Because the oxidation/ reduction and protonation/deprotonation procedures are independent, this system corresponds to switching by orthogonal stimuli. 

Allylation of perfluoroalkyl halides with allylsilanes is catalyzed by iron or ruthenium carbonyl complexes [77S] (equation 119) Alkenyl-, allyl-, and alkynyl-stannanes react with perfluoroalkyl iodides 111 the presence ot a palladium complex to give alkenes and alkynes bearing perfluoroalkyl groups [139] (equation 120)... 

Fig. 17 Indenyl-ruthenium(II) tr-alkynyl complexes generated from allenylidenes...

Since the first discovery of transition metal allenylidene complexes (M=G=C=C<) in 1976, " these complexes have attracted a great deal of attention as a new type of organometallic intermediates. Among a variety of such complexes, cationic ruthenium allenylidene complexes Ru =C=C=GR R, readily available by dehydration of propargylic alcohols coordinated to an unsaturated metal center, can be regarded as stabilized propargylic cation equivalents because of the extensive contribution of the ruthenium-alkynyl resonance form... 

For ruthenium catalysts a detailed study of [(PP3)RuH2] proposes a bis(alkynyl) complex as the real catalyst. The catalytic key step involves the protonation of an alkynyl ligand by external PhC=CH, allowing subsequent C-C bond formation between cis vinylidene and alkynyl groups [9]. 

Cp Ru [14] and TpRu [20] complexes have also been studied in depth. As represented in Scheme 2c, the catalytic alkyne dimerization proceeds via coordinatively unsaturated ruthenium alkynyl species. Either a direct alkyne insertion and/or previous vinylidene formation are feasible pathways that determine the selectivity. The head-to-tail dimer cannot be formed by the vinylidene mechanism, whereas the E or Z stereochemistry is controlled by the nature of the alkynyl-vinylidene coupling. 

The ruthenium allenylidene complexes W are excellent precursors for the catalytic dimerization of tributyltin hydride under mild conditions [ 109] (Eq. 15). In the presence of Bu3SnH, the hydride addition at Cy provides a catalytically active alkynyl ruthenium-tin species (Scheme 22). 

Reductively induced alterations from cumulenic to alkynyl resonance structures have been observed for mononuclear and dinuclear ruthenium allenylidene complexes. The half-wave potentials for the one-electron reduction of allenylidene complexes [ Ru = C = C = C(ER )(R )] ( Ru = trun.s-Cl(L2)2Ru L2 = chelating diphosphine ER = NR2, SR, SeR, aryl, alkyl R = aryl, alkyl) strongly depends on the nature of the ER substituent. Amino- and aryl-substituted congeners with reduction potentials of ca. -2.2 V and -1.0 V, respectively, constitute the two extremes within this series. These sizable potential... 

Abstract The NLO properties of iron, ruthenium, osmium, nickel, and gold alkynyl complexes and... 

Table 1. Molecular second-order NLO results for selected iron, ruthenium and osmium alkynyl complexes ...

The metal centres in the iron, ruthenium, and osmium alkynyl complexes listed in Table 1 possess 18 valence electrons. Table 2 contains HRS data at 1.064 p,m and two-level-corrected values for similar 18 valence electron alkynyl and chloro nickel complexes, and a particularly efficient example is illustrated in Figure 5. These data are substantially resonance enhanced, although the relative orderings are maintained with two-level-corrected values. 

These alkynyl complexes can be protonated to afford vinylidene complexes, which can in turn be deprotonated to give the starting alkynyl complex, reactions that are spectroscopically quantitative. The tabulated data also provide the opportunity to assess the effect of this protonation, in proceeding from alkynyl complex to vinylidene derivative. One would perhaps expect that replacing the electron-rich ruthenium donor in the alkynyl complexes with a (formally) cationic ruthenium centre in the vinylidene complexes would result in a significant decrease in nonlinearity. 

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