Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2]

doi:10.1021/om00060a014

Title: Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2]

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Abstract

The reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 4](CO)[sub 13]([mu]-H)[sub 2] at 97[degrees]C yielded the new decanuclear platinum-ruthenium carbonyl cluster complex Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2] 1 (22%). In a similar manner the reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 3]Pt(CO)[sub 10](COD)([mu]-H)[sub 2], 2, in 25% yield. Both compounds were characterized by IR, [sup 1]H NMR, and single-crystal X-ray diffraction analyses, and both were bound to consist of similar edge-fused bioctahedral clusters with platinum atoms along the edge-sharing sites. There are strong metal-metal bonds between the apices of the adjacent octahedra. Both compounds are electron deficient, and one of the apical-apical Ru-Ru bonds is unusually short, 2.580 (2) [Angstrom] in 1 and 2.593 (5) [Angstrom] in 2. The hydrides are triply bridging ligands, and these were located and refined crystallographically in 1. The reaction of 1 with 1,2-bis(diphenylphosphino)ethane, dppe, yielded the adduct Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-CO)[sub 2](dppe)([mu]-H)[sub 2], 3, in 12% yield, which was shown to consist of a face-shared bioctahedral cluster of seven ruthenium and two platinum atoms with a ruthenium spike containing the dppe ligand extending from one triruthenium face. Two novel dihapto-triply bridging carbonyl ligands were found to bridge to the ruthenium spike.more »« less

Authors:

Adams, R.D.; Zhaoyang Li; Jauching Lii; Wengan Wu ^[1]

(Univ. of South Carolina, Columbia (United States))

Publication Date:: Tue Dec 01 00:00:00 EST 1992

OSTI Identifier:: 6486832

Resource Type:: Journal Article

Resource Relation:: Journal Name: Organometallics; (United States); Journal Volume: 11:12

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLS; MOLECULAR STRUCTURE; HYDRIDES; PLATINUM COMPLEXES; RUTHENIUM COMPLEXES; ABSORPTION SPECTROSCOPY; CHEMICAL PREPARATION; CHEMICAL REACTION YIELD; CRYSTAL STRUCTURE; ETHANE; LAYERS; NUCLEAR MAGNETIC RESONANCE; PHOSPHINES; X-RAY DIFFRACTION; ALKANES; COHERENT SCATTERING; COMPLEXES; DIFFRACTION; HYDROCARBONS; HYDROGEN COMPOUNDS; MAGNETIC RESONANCE; ORGANIC COMPOUNDS; PHOSPHORUS COMPOUNDS; RESONANCE; SCATTERING; SPECTROSCOPY; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; YIELDS; 400201* - Chemical & Physicochemical Properties

Citation Formats


                    Adams, R.D., Zhaoyang Li, Jauching Lii, and Wengan Wu. Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2].  United States: N. p., 1992. 
        Web.  doi:10.1021/om00060a014.

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                    Adams, R.D., Zhaoyang Li, Jauching Lii, & Wengan Wu. Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2].  United States.  doi:10.1021/om00060a014.

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                    Adams, R.D., Zhaoyang Li, Jauching Lii, and Wengan Wu. Tue .  
        "Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2]".  United States.  doi:10.1021/om00060a014.

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@article{osti_6486832,

  title        = {Cluster synthesis. 40. New high-nuclearity platinum-ruthenium carbonyl cluster complexes. Synthesis and structural characterizations of Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2], Ru[sub 7]Pt[sub 3](CO)[sub 22]([mu][sub 3]-H)[sub 2], and Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-[eta][sup 2]-CO)[sub 2](dppe)([mu]-H)[sub 2] with a new type of triply bridging CO ligand and the new layered cluster complex Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2]},

  author       = {Adams, R.D. and Zhaoyang Li and Jauching Lii and Wengan Wu},

  abstractNote = {The reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 4](CO)[sub 13]([mu]-H)[sub 2] at 97[degrees]C yielded the new decanuclear platinum-ruthenium carbonyl cluster complex Ru[sub 8]Pt[sub 2](CO)[sub 23]([mu][sub 3]-H)[sub 2] 1 (22%). In a similar manner the reaction of Ru[sub 4]Pt[sub 2](CO)[sub 18] with Ru[sub 3]Pt(CO)[sub 10](COD)([mu]-H)[sub 2], 2, in 25% yield. Both compounds were characterized by IR, [sup 1]H NMR, and single-crystal X-ray diffraction analyses, and both were bound to consist of similar edge-fused bioctahedral clusters with platinum atoms along the edge-sharing sites. There are strong metal-metal bonds between the apices of the adjacent octahedra. Both compounds are electron deficient, and one of the apical-apical Ru-Ru bonds is unusually short, 2.580 (2) [Angstrom] in 1 and 2.593 (5) [Angstrom] in 2. The hydrides are triply bridging ligands, and these were located and refined crystallographically in 1. The reaction of 1 with 1,2-bis(diphenylphosphino)ethane, dppe, yielded the adduct Ru[sub 8]Pt[sub 2](CO)[sub 21]([mu][sub 3]-CO)[sub 2](dppe)([mu]-H)[sub 2], 3, in 12% yield, which was shown to consist of a face-shared bioctahedral cluster of seven ruthenium and two platinum atoms with a ruthenium spike containing the dppe ligand extending from one triruthenium face. Two novel dihapto-triply bridging carbonyl ligands were found to bridge to the ruthenium spike. 1 and 2 both react with CO at 25[degrees]C, but only the product obtained from the reaction of 2, Ru[sub 6]Pt[sub 3](CO)[sub 21]([mu]-CO)([mu][sub 3]-H)[sub 2], 4, (55% yields), could be fully characterized. It was shown to contain a cluster of nine metal atoms arranged into trinuclear layers of pure ruthenium and pure platinum. The two triply bridging hydride ligands were located and refined crystallographically. 23 refs., 4 figs., 13 tabs.},

  doi          = {10.1021/om00060a014},

  journal      = {Organometallics; (United States)},

  number       = ,

  volume       = 11:12,

  place        = {United States},

  year         = {Tue Dec 01 00:00:00 EST 1992},

  month        = {Tue Dec 01 00:00:00 EST 1992}

}

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DOI: 10.1021/om00060a014

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Cluster synthesis. 39. New platinum-ruthenium carbonyl cluster complexes with bridging hydride ligands. Synthesis and structural characterizations of Ru sub 4 Pt(CO) sub 13 (COD)(. mu. -H) sub 2 , Ru sub 3 Pt(CO) sub 9 (. mu. -CO)(COD)(. mu. -H) sub 2 , Ru sub 4 Pt sub 2 (CO) sub 11 (COD) sub 2 (. mu. sub 3 -H) sub 2 , and Ru sub 5 Pt sub 5 (CO) sub 18 (COD) sub 2 (. mu. -H) sub 2 , COD = Cycloocta-1,5-diene

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The authors have recently discovered that bis(dialkylamino)-methane compounds are effective reagents for the introduction of secondary (dialkylamino)carbene ligands into osmium carbonyl clusters. They have now examined the reaction of Os/sub 3/(CO)/sub 10/(..mu..-H)/sub 2/ with CH/sub 2/(NMe)/sub 2/. This reaction yields initially the new compound Os/sub 3/(CO)/sub 10/(..mu..-eta/sup 2/-H/sub 2/CNMe/sub 2/)(..mu..-H) which can be transformed into the compounds Os/sub 3/(CO)/sub 9/(..mu../sub 3/-eta/sup 2/-C(H)NMe/sub 2/)(..mu..-H)/sub 2/ and Os/sub 3/(CO)/sub 10/(..mu..-CNMe/sub 2/)(..mu..-H) through a sequence of C-H activation processes in the (dimethylamino)methyl group. The results of these studies are reported herein.
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