The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

Salter, Ian D.

doi:10.1002/9783527618316.ch1aa

Cited by 3 publications

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References 28 publications

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“…Synthesis of mixed metal cluster compounds of different composition and geometry is a challenging area of inorganic chemistry that has attracted considerable attention from the very early stage of cluster chemistry 1-3 until the present day. [4][5][6][7] The elaboration of effective approaches to the synthesis of heterometallic complexes and the understanding of the reaction mechanisms can open up opportunities for the use of these compounds in academic research and applied chemistry, mainly in the field of homogeneous and heterogeneous catalysis. 4,8-11 Platinum-ruthenium and palladium-ruthenium carbonyl cluster complexes are among the most effective precursors for bimetallic nanoparticles that have been used as highly active hydrogenation catalysts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

et al. 2006

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A novel trimetallic cluster [Ru5CRh2Pt2(CO)16(dppm)2] was synthesized via coupling of two neutral clusters-[Ru5C(CO)15] and [Rh2Pt2(CO)6(dppm)2]. The structure of this mixed metal complex was established using X-ray crystallography and 31P NMR spectroscopy. It was found that the reaction between [Ru6C(CO)17] and [Pt2(CO)3(dppm)2] leads to spontaneous electron transfer between these polynuclear complexes and results in the formation of an unusually stable cluster "salt" {[Ru6(CO)16]2-[Pt2(CO)2(dppm)2]2+}, which was characterized by crystallographic and spectroscopic methods. Heating of the Ru6-Pt2 ion pair in an autoclave (145 degrees C, 15 atm N2) results in fusion of the metal frameworks to give a nonanuclear mixed metal [Ru6C(CO)16Pt3(dppm)2] cluster in a good yield. The latter complex was obtained earlier as a minor product of another thermal reaction and now has been additionally characterized by 31P NMR spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

et al. 2006

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Remarkable Dynamical Opening and Closing of Platinum and Palladium Pentaruthenium Carbido Carbonyl Cluster Complexes

Adams

Captain

et al. 2003

Inorg. Chem.

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The reaction of Ru(5)(CO)(15)(mu(5)-C), 1, with Pt(PBu(t)(3))(2) at room temperature yielded the mixed-metal cluster complex PtRu(5)(CO)(15)(PBu(t)(3))(C), 2, in 52% yield. Compound 2 consists of a mixture of two interconverting isomers in solution. One isomer, 2A, can be isolated by crystallization from benzene/octane solvent. The second isomer, 2B, can be isolated by crystallization from diethyl ether. Both were characterized crystallographically. Isomer 2A consists of a square pyramidal cluster of five ruthenium atoms with a phosphine-substituted platinum atom spanning the square base. Isomer 2B consists of a square pyramidal cluster of five ruthenium atoms with a phosphine-substituted platinum atom on an edge on the square base. The two isomers interconvert rapidly on the NMR time scale at 40 degrees C, deltaG(313)++ = 11.4(8) kcal mol(-1), deltaH++ = 8.8(5) kcal mol(-1), deltaS++ = -8.4(9) cal mol(-1) K(-1). The reaction of Pd(PBu(t)(3))(2) with compound 1 yielded two new cluster complexes: PdRu(5)(CO)(15)(PBu(t)(3))(mu(6)-C), 3, in 50% yield and Pd(2)Ru(5)(CO)(15)(PBu(t)(3))(2)(mu(6)-C), 4, in 6% yield. The yield of 4 was increased to 47% when an excess of Pd(PBu(t)(3))(2) was used. In the solid state compound 3 is structurally analogous to 2A, but in solution it also exists as a mixture of interconverting isomers; deltaG(298)++ = 10.6(6) kcal mol(-1), deltaH++ = 9.7(3) kcal mol(-1), and deltaS++ = -3(1) cal mol(-1) K(-1) for 3. Compound 4 contains an octahedral cluster consisting of one palladium atom and five ruthenium atoms with an interstitial carbido ligand in the center of the octahedron, but it also has one additional Pd(PBu(t)(3)) grouping that is capping a triangular face of the ruthenium cluster. The Pd(PBu(t)(3)) groups in 4 also undergo dynamical interchange that is rapid on the NMR time scale at 25 degrees C; deltaG(298)++ = 11(1) kcal mol(-1), deltaH++ = 10.2(4) kcal mol(-1), and deltaS++ = -3(2) cal mol(-1) K(-1) for 4.

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Generation of AuPd₂₂/Au₂Pd₂₁analogues of the high-nuclearity Pd₂₃(CO)₂₀(PEt₃)₁₀cluster containing 19-atom centered hexacapped-cuboctahedral (ν₂-octahedral) metal fragment: structural-to-synthesis approach concerning formation of Au₂Pd₂₁(CO)₂₀(PEt₃)₁₀

2004

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Reactions of Pd(PEt(3))(2)Cl(2) and Au(PPh(3))Cl in DMF with NaOH under CO atmosphere gave rise to the unique capped three-shell homopalladium Pd(145)(CO)(x)(PEt(3))(30)(x approximately 60) and two neutral Au-Pd clusters: Au(2)Pd(21)(CO)(20)(PEt(3))(10) (1) and Au(2)Pd(41)(CO)(27)(PEt(3))(15)(following article). Similar reactions with Pd(PMe(3))(2)Cl(2) being used in place of Pd(PEt(3))(2)Cl(2) afforded Au(2)Pd(21)(CO)(20)(PMe(3))(10) (2), the trimethylphosphine analogue of, and the electronically equivalent [AuPd(22)(CO)(20)(PPh(3))(4)(PMe(3))(6)](-) monoanion (3) as the [PPh(4)](+) salt. Each of these three air-sensitive 23-atom heterometallic Au-Pd clusters was obtained in low yields (7-25%); however, their geometrical similarities with the known cuboctahedral-based homopalladium Pd(23)(CO)(20)(PEt(3))(10) (4), recently obtained in good yields from Pd(10)(CO)(12)(PEt(3))(6), suggested an alternative preparative route for obtaining. This "structure-to-synthesis" approach afforded 1 in 60-70% yields from reactions of Pd(10)(CO)(12)(PEt(3))(6) and Au(PPh(3))Cl in DMF with NaOH under N(2) atmosphere. Both the compositions and atomic arrangements for 1, 2 and 3 were unambiguously established from low-temperature single-crystal CCD X-ray crystallographic determinations in accordance with their nearly identical IR carbonyl frequencies. Cluster 1 was also characterized by (31)P[(1)H] NMR, cyclic voltammetry (CV) and elemental analysis. The virtually identical Au(2)Pd(21) core-architectures of 1 and 2 closely resemble that of 4, which consists of a centered hexa(square capped)-cuboctahedral Pd(19) fragment of pseudo-O(h) symmetry that alternatively may be viewed as a centered Pd(19)nu(2)-octahedron (where nu(n) designates (n + 1) equally spaced atoms along each edge). [AuPd(22)(CO)(20)(PPh(3))(4)(PMe(3))(6)](-) (3) in the crystalline state ([PPh(4)](+) salt) consists of two crystallographically independent monoanions 3A and 3B; a superposition analysis ascertained that their geometries are essentially equivalent. A CV indicates that reversibly undergoes two one-electron reductions and two one-electron oxidations; these reversible redox processes form the basis for an integrated structural/electronic picture that is compatible with the existence of the electronically-equivalent 1-3 along with the electronically-nonequivalent 4 (with two fewer CVEs) and other closely related species.

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The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

Cited by 3 publications

References 28 publications

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

Remarkable Dynamical Opening and Closing of Platinum and Palladium Pentaruthenium Carbido Carbonyl Cluster Complexes

Generation of AuPd₂₂/Au₂Pd₂₁analogues of the high-nuclearity Pd₂₃(CO)₂₀(PEt₃)₁₀cluster containing 19-atom centered hexacapped-cuboctahedral (ν₂-octahedral) metal fragment: structural-to-synthesis approach concerning formation of Au₂Pd₂₁(CO)₂₀(PEt₃)₁₀

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The Heteronuclear Cluster Chemistry of the Group 11 Metals – Some Recent Advances

Cited by 3 publications

References 28 publications

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru6(CO)16]2−[Pt2(CO)2(dppm)2]2+ion pair on the way to [Ru6C(CO)16Pt3(dppm)2]

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru6(CO)16]2−[Pt2(CO)2(dppm)2]2+ion pair on the way to [Ru6C(CO)16Pt3(dppm)2]

Remarkable Dynamical Opening and Closing of Platinum and Palladium Pentaruthenium Carbido Carbonyl Cluster Complexes

Generation of AuPd22/Au2Pd21analogues of the high-nuclearity Pd23(CO)20(PEt3)10cluster containing 19-atom centered hexacapped-cuboctahedral (ν2-octahedral) metal fragment: structural-to-synthesis approach concerning formation of Au2Pd21(CO)20(PEt3)10

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Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru₆(CO)₁₆]²⁻[Pt₂(CO)₂(dppm)₂]²⁺ion pair on the way to [Ru₆C(CO)₁₆Pt₃(dppm)₂]

Generation of AuPd₂₂/Au₂Pd₂₁analogues of the high-nuclearity Pd₂₃(CO)₂₀(PEt₃)₁₀cluster containing 19-atom centered hexacapped-cuboctahedral (ν₂-octahedral) metal fragment: structural-to-synthesis approach concerning formation of Au₂Pd₂₁(CO)₂₀(PEt₃)₁₀