Cluster Synthesis. 43. New Layer-Segregated Platinum-Ruthenium Cluster Complexes and Their Reactions with Diphenylacetylene

Adams, Richard D.; Barnard, Thomas S.; Li, Zhaoyang; Wu, Wengan; Yamamoto, John H.

doi:10.1021/om00018a030

Cited by 34 publications

(39 citation statements)

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“…The promising approach to enantioselective hydrogenation by use of chiral metal frameworks or of chiral polydentate ligands on clusters has been explored with limited success, but developments of possible utility are yet to be realized; continued efforts in that direction are certainly worthwhile. Heterobimetallic clusters appear as good candidates for promoting reactions not catalyzed by a single metal through synergistic enhancement of the properties of individual components; some interesting examples are now available where bimetallic high-nuclearity cluster catalysis has been demonstrated, and applications to unusual reactions are to be expected [4,[53][54][55][56]. The use of defined clusters as precursors of nanostructured materials is also of great interest, even if it falls outside the field of homogeneous hydrogenation.…”

Section: Discussionmentioning

confidence: 99%

“…More recently, Adams and coworkers have provided a very interesting case of heteronuclear clusters that are very active for the hydrogenation of alkynes [4,54,55]. The high-nuclearity layer-segregated Pt-Ru complex [Pt 3 Ru 6 (CO) 21 alternating arrangement Ru 3 Pt 3 Ru 3 , readily reacts with diphenylacetylene to yield an alkyne complex, according to Eq.…”

Section: Hydrogenation Of CC Bondsmentioning

confidence: 99%

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Homogeneous Hydrogenation by Defined Metal Clusters

Sánchez‐Delgado¹

2006

The Handbook of Homogeneous Hydrogenation

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The catalytic potential of well-defined transition-metal clusters in homogeneous reactions has attracted a great deal of attention over the years, as they represent a natural bridge between mononuclear complexes, metal nanoparticles, and metal-oxide, -sulfide and related surfaces used in heterogeneous catalysis. The molecular nature of metal clusters, together with their solubility properties, provides the advantages of classical mononuclear homogeneous catalysts (high activity, high selectivity, moderate operating conditions, possibility of catalyst design and modification), while the polynuclear framework can offer the possibility of multi-metallic cooperative effects often identified as a key element in the desirable properties of solid heterogeneous catalysts. Therefore, metal clusters can be expected, in principle, to combine the positive aspects of homogeneous and heterogeneous catalytic reactions and, perhaps more importantly, they may react through unique pathways associated with the cluster structures and thereby catalyze reactions not accessible by mononuclear or heterogeneous catalysts. Nevertheless, despite the impressive amount of work that has been devoted to develop these concepts over several decades, the great expectations first advanced during the mid-1970s have not yet been fully accomplished [1][2][3][4][5][6].From a different perspective, well-defined metal clusters have served as useful models for discerning the complex mechanisms of heterogeneous catalytic systems. The structural trends for metal clusters are now well understood, and their reactions in solution can be studied in detail by relatively simple chemical and spectroscopic methods, thereby producing important information at the molecular level -something that is very difficult to achieve on solid catalysts. The knowledge thus gained from studying metal cluster chemistry can be extrapolated, with adequate caution, to heterogeneous reactions [1][2][3][4][5][6].Another trend that has received considerable recent attention is the decomposition of metal clusters under controlled conditions on solid supports or on liquid suspensions, which generates small metallic particles of specific size, struc- 199The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier

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Section: Discussionmentioning

confidence: 99%

Section: Hydrogenation Of CC Bondsmentioning

confidence: 99%

Homogeneous Hydrogenation by Defined Metal Clusters

Sánchez‐Delgado¹

2006

The Handbook of Homogeneous Hydrogenation

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“…The Pt-Pt, Pt-Ru, and Ru-Pt interactions were calculated from crystallographic data reported for metallic platinum [13] and [PtRu 2 (CO) 8 (dppe)] (dppe is 1,2-bis (diphenylphosphino)ethane) [14]. As there are hydride ligands on the ruthenium in the precursor Pt 3 Ru 6 (CO) 21 (l 3 -H)(l-H) 3 , the Ru-Ru interaction for the reference was calculated from crystallographic data characterizing a compound with such ligands, Pt 3 Ru 6 (CO) 21 (l 3 -H)(l-H) 3 [15]. The reference Pt-Mg interaction was generated from crystallographic data characterizing MgPt 3 [16].…”

Section: Exafs Data Analysismentioning

confidence: 99%

“…We infer that in each sample the metal clusters were bonded rather strongly to the support, as indicated by the significant metal-oxygen Table 1 Summary of structural data characterizing crystalline Pt 3 Ru 6 (CO) 21 (l 3 -H)(l-H) 3 [15] and samples formed from this cluster on MgO and c-Al 2 O 3 [4] after treatment in He at 300°C for 2 h Edge Shell XRD data characterizing …”

Section: Structures Of the Bimetallic Clustersmentioning

confidence: 99%

MgO-supported cluster catalysts with Pt–Ru interactions prepared from Pt3Ru6(CO)21(μ3-H)(μ-H)3

et al. 2007

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Bimetallic MgO-supported catalysts were prepared by adsorption of Pt 3 Ru 6 (CO) 21 (l 3 -H)(l-H) 3 on porous MgO. Characterization of the supported clusters by infrared (IR) spectroscopy showed that the adsorbed species were still in the form of metal carbonyls. The supported clusters were decarbonylated by treatment in flowing helium at 300°C, as shown by IR and extended X-ray absorption fine structure (EXAFS) data, and the resulting supported PtRu clusters were shown by EXAFS spectroscopy to have metal frames that retained Pt-Ru bonds but were slightly restructured relative to those of the precursor; the average cluster size was almost unchanged as a result of the decarbonylation. These are among the smallest reported bimetallic clusters of group-8 metals. The decarbonylated sample catalyzed ethylene hydrogenation with an activity similar to that reported previously for c-Al 2 O 3 -supported clusters prepared in nearly the same way and having nearly the same structure. Both samples were also active for n-butane hydrogenolysis, with the MgO-supported catalyst being more active than the c-Al 2 O 3 -supported catalyst.

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“…Compound 9 reacts with hydrogen to produce the layer-segregated cluster Pt 3 Ru 6 (CO) 21 (l 3 -H)(l-H) 3 (10) that contains a triangular group of three platinum atoms sandwiched between to ruthenium triangles [36]. Compound 10 exhibits very interesting reactivity toward alkynes [37] and was shown to be a good catalyst of the hydrogenation of PhC 2 Ph to Z-stilbene, see below.…”

Section: Bridging Alkylidyne Ligandsmentioning

confidence: 99%