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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]

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 » 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.« less

Authors:
; ; ;  [1]
  1. (Univ. of South Carolina, Columbia (United States))
Publication Date:
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.
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.
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.
@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}
}