Reactions of metalloalkynes

Transformation of C2 units on a bimetallic tetranuclear cluster.

“…By contrast 9b, the all (g-C 5 H 4 Me) compound, crystallises in space group Cmca with only one metal atom in the asymmetric unit and is not disordered. The solid state structures resemble those of the previously described permetallated ethene complexes [Ru 2 (CO) 8 Ru 2 (g-C 5 H 4 R) 2 (l-CO) 2 (l 4 -C 2 )] (R = H, 5a; Me, 5b) [1,2] and [Ru 2 (CO) 8 Fe 2 (g-C 5 Me 5 ) 2 (l-CO) 2 (l 4 -C 2 )] (6) [31], along with the 68 cluster valence electron (CVE) complex [{Ru 2 (CO) 6 (l-PPh 2 )} 2 (l 4 -C 2 )] (7) [32]. Unlike these latter complexes, a distortion of the present M 4 rectangular array is not evident as seen from the essentially identical separation of the opposing vertices between the two dinuclear fragments of 4.4191(7) Å (Ru(1)-Ru(3)) and 4.4291(7) Å (Ru(2)-Mo (4)).…”

“…A number of complexes similar to these have been previously described as permetallated ethene complexes, by us in the form [Ru 4 (l 4 -C 2 )(l-CO) 2 (CO) 8 (g-C 5 H 4 R) 2 ] (R = H, 5a; Me, 5b) [1,2] and by Japanese workers in the analogous [Ru 2 Fe 2 (l 4 -C 2 )(l-CO) 2 (CO) 8 -(g-C 5 Me 5 ) 2 ] (6) [31], along with the 68 cluster valence electron (CVE) complex [{Ru 2 (CO) 6 (l-PPh 2 )} 2 (l 4 -C 2 )] (7) [32]. We found that the reaction of [{Ru(CO) 2 (g- …”

“…We have been examining the reactivity of C 2 -containing complexes over recent years to assist our understanding of the transformation of catalytically relevant species and their use in templating the formation of larger metal aggregates in a rational manner [1][2][3][4][5][6][7]. In recent reports we have recorded the synthesis of a mixed metal cluster [Ru 3 Mo(l 4 -g 2 -CC)(l-CO) 3 (CO) 2 (g-C 5 H 4 R) 3 (g-C 5 H 5 )] (R = H, 1a; Me, 1b) [4,5], supported by spectroscopic and single crystal X-ray studies, the key feature of interest being the distribution of the two types of metal atom within a skeleton readily defined as comprising a triangular metal cluster coupled to the fourth metal atom by the carbide group: [{(g-C 5 H 4 R) 3 (l-CO) 3 M 3 }CC{M(CO) 2 (g-C 5 H 5 )}].…”

A Linear Ru‐Tl‐Ru Complex Obtained from Halide Abstraction: An Example of Metal‐Dative Bonding

“…In recent work, we have been pursuing the chemistry of the Ru(CO) 2 (η-C 5 H 5 ) fragment in various guises [10][11][12][13][14][15][16][17][18][19] and have observed that protonation of [{Ru(CO) 2 (η-C 5 H 5 )} 2 (µ-CϵC)] gave the unexpected trinuclear complex, [{Ru(CO) 2 -(η-C 5 H 5 )} 3 (µ-CϵC)] + . [16] This reaction was irreproducible, but the nature of the product suggested that a more rational and dependable route to its synthesis was the addition of the metal electrophile [Ru(CO) 2 (η-C 5 H 5 )(solvent)] + to [{Ru(CO) 2 (η-C 5 H 5 )} 2 (µ-CϵC)].…”

Flexible Platinum(0) Coordination to a Ditungsten Ethanediylidyne

“…[13] Ther esulting orange product, [W 2 (m-C 2 Au 2 Cl 2 )(CO) 4 (Tp*) 2 ]( 8), contains two AuCl fragments transversely added across both WCb onds and, being much more soluble than 7,i sm ore amenable to complete spectral and structural characterization ( Figure 3a nd the Supporting Information). Thef ew known tetra-metalated dicarbido assemblies all adhere to ethyn-di-yl [14] or ethen-tetra-yl [15] bonding descriptions that retain ad egree of CÀCm ultiple bonding.T he exception, [Fe 2 Ru 2 (m 4 -C 2 )(CO) 8 (m-PhCCPh)-(Cp*) 2 ] [16] may be described as involving Ru=Ca nd Ru=Ru Figure 2. Molecular structure of 4 in acrystal of 4•CH 2 Cl 2 (ellipsoids set at 50 %p robability,h ydrogen atoms and solvent omitted,p yrazolyl rings simplified).…”