Cluster Complexes with Bonds Between Transition Elements and Copper, Silver and Gold

Salter, Ian D.

doi:10.1016/b978-008046519-7.00089-7

Cited by 13 publications

(3 citation statements)

References 335 publications

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“…One highly active area in metal cluster chemistry during the last two decades has involved the preparation of mixed transition metal−gold clusters and examination of their physical-chemical properties . A large number of cationic transition metal−gold clusters have been prepared by Pignolet and co-workers 3 from reactions of Au(PPh 3 )NO 3 with transition metal phosphine complexes containing a group VIII (8−10) metal (with the notable exception of Ni).…”

Section: Introductionmentioning

confidence: 99%

Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

et al. 1999

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Efforts to obtain large trimetallic Au−Pd−Ni carbonyl clusters have given rise to the first reported high-nuclearity trimetallic carbonyl cluster [Au6Pd6(Pd6 - x Ni x )Ni20(CO)44]6- (1). The centrosymmetric architecture of its 38-atom core ideally consists of the hcp stacking of two inner Au3M3Ni6 and two outer Pd3 layers along with two Pd3-capped and six AuNi2-capped Ni atoms. The resulting octahedral-like Au6 kernel is antiprismatically capped on opposite triangular faces by the two Pd3 triangles. The microscopic nature of its nonstoichiometric composition was unequivocally established from complete X-ray diffraction analyses via a SMART CCD system of seven crystals of its [PPh4]+ salt from different samples. A substitutional Pd/Ni crystal disorder was found at only six specific nonadjacent atomic M sites (three crystallographically independent); for the composite six-site crystal disorder of the (6 − x) Pd/x Ni atoms, x was determined for the seven crystals to range from 2.1 (65% Pd, 35% Ni) to 5.5 (8% Pd, 92% Ni). The overall geometry of 1 including the 44 CO ligands (in the crystal-averaged unit cell) ideally has trigonal D 3 d (3̄2/m) symmetry. A structure/bonding analysis as to why this particular Pd/Ni substitutional crystal disorder is found in 1 provides a striking illustration that the occurrence of a bimetallic substitutional crystal disorder at only certain crystallographic sites (coloring problem) in a heterometallic carbonyl cluster is critically dependent upon the extent of dissimilarity in the composite relative bond-energy effects of metal−metal/metal−CO interactions. 1 was obtained as a major product (35−40% yields) from reactions of [Ni6(CO)12]2- with Pd(OAc)2/Au(PPh3)Cl mixtures in DMSO. Our desire to obtain the hypothetical isostructrual [Au6Ni32(CO)44]6- (2), in which all Pd atoms are replaced with Ni ones, led to the designed synthesis and structural determination of 2, which in turn provided an “operational test” of our “coloring-problem” analysis of 1. The maximum metal-core diameters in 1 and 2 are ca. 1.1 nm parallel and 0.8 nm perpendicular to the principal 3-fold axis.

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Section: Introductionmentioning

confidence: 99%

Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

et al. 1999

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“…Since the publication of the seminal work of Nyholm and Lewis − in 1964, a great number of homo- and heteronuclear gold complexes containing direct metal−metal bonds have been described. Most of them are either clusters with the gold having a formal oxidation state between 0 and 1 or, alternatively, polynuclear complexes containing up to six Au(PR 3 ) units in the molecule, being gold(I) derivatives …”

Section: Introductionmentioning

confidence: 99%

Tris(amido)tingold Complexes in Different Oxidation States. First Structural Characterization of a Sn−Au−Au−Sn Linear Chain

et al. 1997

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The reaction of [MeSi{Me(2)SiN(Li)(p-tol)}(3)(Et(2)O)(2)] with SnCl(2) in a 1:1 molar ratio leads the tris(amido)stannate [MeSi{Me(2)SiN(p-tol)}(3)SnLi(Et(2)O)] (1), which further reacts with neutral [AuCl(PPh(3))] and anionic [PPN][AuCl(2)], PPN[AuRCl] (R = C(6)F(5), mes), and chlorogold(I) complexes yielding [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(PPh(3))] (2) and [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (3) and [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(R)] (R = C(6)F(5), 4; R = mes, 5), respectively. The reaction of 1 with the dinuclear gold(II) derivative [Au(2)(CH(2)PPh(2)CH(2))(2)Cl(2)] in a 1:2 ratio affords [Au(2)(CH(2)PPh(2)CH(2))(2)(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (6). In a similar way but starting from PPN[Au(C(6)F(5))(3)Cl] and reacting with 1 in a 1:1 ratio, the Au(III) complex [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(C(6)F(5))(3)] (7) has been obtained. X-ray crystal structure analyses were performed for compounds 2 and 6, establishing the Sn-Au bonds [d(Au-Sn) = 2.5651(13) and 2.6804(13) Å, respectively). Compound 6 has a nearly linear Sn-Au-Au-Sn array and features the first examples of tin-gold(II) bonds.

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“…A great number of heterometallic gold− or mercury−iron clusters have been synthesized by the condensation reactions of polyiron anionic carbonyl clusters with the cationic fragments AuPR 3 + and HgM + (M = a metal fragment, such as Mo(CO) 3 Cp) . In these species the electrophilic fragments AuPR 3 + and HgM + bridge edges or, less frequently, cap faces of the iron polyhedron.…”

Section: Introductionmentioning

confidence: 99%

Selective Additions of Group 11 and 12 Metal Fragments to the Fe₄C and Fe₅C Units

et al. 2000

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A selective site of interaction has been observed in reacting HgM + or M′PPh 3 + (M ) Mo(CO) 3 Cp, W(CO) 3 Cp; M′ ) Au, Cu, Ag) with [Fe 4 C(CO) 12 {HgM}]to give the mixedtransition-metal clusters [Fe 4 C(CO) 12 {HgM} 2 ] and [Fe 4 C(CO) 12 {HgM}{M′PPh 3 }], respectively. The reaction of [Fe 5 C(CO) 14 {HgM}]with M′PPh 3 + permits us to obtain the very unstable neutral octanuclear [Fe 5 C(CO) 14 {HgM}{M′PPh 3 }] clusters. The new compounds have been studied by VT-NMR and Mo ¨ssbauer spectroscopy. The electrochemical behavior of the Fe 4 C derivatives has been investigated, and an X-ray crystal structure determination of the complex [Fe 4 C(CO) 12 {HgMo(CO) 3 Cp}{AuPPh 3 }] has been carried out.

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Cluster Complexes with Bonds Between Transition Elements and Copper, Silver and Gold

Cited by 13 publications

References 335 publications

Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Tris(amido)tingold Complexes in Different Oxidation States. First Structural Characterization of a Sn−Au−Au−Sn Linear Chain

Selective Additions of Group 11 and 12 Metal Fragments to the Fe₄C and Fe₅C Units

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Cluster Complexes with Bonds Between Transition Elements and Copper, Silver and Gold

Cited by 13 publications

References 335 publications

Isostructural [Au6Pd6(Pd6-xNix)Ni20(CO)44]6-and [Au6Ni32(CO)44]6-Clusters Containing Corresponding Nonstoichiometric Au6Pd6(Pd6-xNix)Ni20and Stoichiometric Au6Ni32Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Isostructural [Au6Pd6(Pd6-xNix)Ni20(CO)44]6-and [Au6Ni32(CO)44]6-Clusters Containing Corresponding Nonstoichiometric Au6Pd6(Pd6-xNix)Ni20and Stoichiometric Au6Ni32Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Tris(amido)tingold Complexes in Different Oxidation States. First Structural Characterization of a Sn−Au−Au−Sn Linear Chain

Selective Additions of Group 11 and 12 Metal Fragments to the Fe4C and Fe5C Units

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Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Isostructural [Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀(CO)₄₄]⁶^-and [Au₆Ni₃₂(CO)₄₄]⁶^-Clusters Containing Corresponding Nonstoichiometric Au₆Pd₆(Pd₆_-xNi_x)Ni₂₀and Stoichiometric Au₆Ni₃₂Nanosized Cores: Substitutional Pd/Ni Crystal Disorder (Coloring Problem) at

Selective Additions of Group 11 and 12 Metal Fragments to the Fe₄C and Fe₅C Units