Hetero‐metallic clusters. Synthesis and characterization of [PtAu8 (PPh3)8] (NO3)2 and [HPtAu7(PPh3)8](NO3)2

Bour, J. J.; Kanters, R. P. F.; Schlebos, P. P. J.; Bosman, W. P.; Behm, H.; Beurskens, Paul T.; Steggerda, J. J.

doi:10.1002/recl.19871060504

Cited by 36 publications

(12 citation statements)

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“…Selected bond lengths for [M@Au 8 (PPh 3 ) 8 ] n+ ( I ), [M@HgAu 8 (PPh 3 ) 8 ] n+ ( II ), and [M@Hg 2 Au 8 (PPh 3 ) 8 ] n+ ( III ) (M = Pd, Pt, n = 2; M = Au, n = 3) are given in Table . The obtained structures (Figure ) are in agreement with the available previous experimental data (Table ) . For [Pd@Au 8 L 8 ] 2+ and [Pt@Au 8 L 8 ] 2+ , the crown‐motif of the core remains in both solution and solid states .…”

Section: Resultssupporting

confidence: 90%

See 1 more Smart Citation

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Quintana

Ocayo

Guajardo‐Maturana

et al. 2019

Int J of Quantum Chemistry

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Superatomic clusters offer useful templates displaying distinctive physical and chemical characteristics. Here, we explore the [M@Au 8 (PPh 3 ) 8 ] n+ (M = Au, n = 3; Pd, Pt, n = 2) robust framework to gain an understanding of the nature of the inclusion of mercury atoms at Au 4 faces, leading to [M@Au 8 Hg x (PPh 3 ) 8 ] n+ (x = 1, 2). Our results show a weak interaction of about 25 kcal mol −1 per Hg atom, which is mainly of electrostatic character, followed by orbital and London dispersion-type interactions. This weak interaction can be understood as the formation of host-guest species, for which the inherent electronic and optical properties of the [M@Au 8 (PPh 3 ) 8 ] cluster along the series do not vary to a large extent. This demonstrates that, in [M@Au 8 Hg x (PPh 3 ) 8 ], each Hg can be considered an inclusion atom rather than a dopant element, where the parent cluster is able to act as a Lewis acid host. Furthermore, the viable formation of such species can serve as useful examples to stimulate future experimental characterization of inclusion complexes involving related superatomic structures with available open faces. K E Y W O R D S clusters, gold clusters, Lewis-acid, mercury

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Section: Resultssupporting

confidence: 90%

“…This contrast is observed when using larger counteranions (PMo 12 O 40 ), which retain the crown core in solid state . It is important to note that the incorporation of Pd and Pt atoms can hinder such an isomerization process …”

Section: Resultsmentioning

confidence: 99%

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Quintana

Ocayo

Guajardo‐Maturana

et al. 2019

Int J of Quantum Chemistry

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“…�� Ru3 f�� of �� o��o� �� pp��g b� P�(�o�) u��. W�� P�3Ru3 o��o� �� P��P� bo�� g� 2.6327 (7) �� u��u�� of ��o�� b�o�� P� 3 Ru 6 (µ 3 �η 2 �P�C≡CP�) 3 (CO) 18 [9] �� b� �� omb��o� of �� M 4 ��. ��o of �� o�� , P�(1)P�(2)Ru(3)Ru(4) �� P�(2)P�(3) Ru(5)Ru (6).…”

Section: Heterononanuclear Pt Clustersunclassified

Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

2014

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This review classifies and analyses fifty heteronona- and heterodecanuclear Pt clusters of metal composition: Pt4Ru5, Pt3Ru6, Pt20sr PtRh8, PtAu8; Pt6M4, Pt5M5, Pt4M6, Pt3M2, Pt2M8, PtM9, Pt3Ru6M and PtAu8M. There are nine different heterometals: M = Ru, Au, Ag, Cu, Hg, Os, Rh, Ir and Fe, of which Ru and Au are the most frequent. The clusters crystallize mostly into two crystal classes, monoclinic (74%) and triclinic (18%), and their structures are complex. Three triangular layers of nine metal atoms arranged in the form of a face-shared bioctahedron are common in the series of heterononanuclear clusters. In the series of heterodecanuclear clusters distorted skeletal icosahedrons, where a central platinum atom is surrounded by nine metal atoms, and face (edge) shared (fused) bioctahedral cluster of the metal atoms are the most common. The most frequent ligands are CO and PPh3. The shortest metal-metal bond distances are: 2.540(4) Å (Pt-Fe), 2.580(2) Å (Ru-Ru), 2.584 Å (Pt-Pt) and 2.629(4) Å (Cu-Au). Several relationships between the structural parameters were found and are discussed. Some clusters contain two crystallographically independent molecules within the same crystal and are examples of distortion isomerism.

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“…106.16 (6) 57.72(4) 57.8 l(7) 106.37 (6) 60.03(5) 5 5. (5) 56.55( 4) (5) 57.49 (7) Rh-A~(7)-Au (3) 56.97(7) Rh-A~(7)-Au (5) 56.7 l(6) R h-A u ( ~)-Au( 8 67.24(8) Au( 6)-Rh-A~(5) 11 1.9(1) Au( 7)-Rh-A~ (2) 114.6(1) Au( 7)-Rh-A~(4) 6 1.25( 7) Au( 7)-R h-Au ( 6) 60.99( 7) Au( 8)-Rh-A~ (2) 59.90( 7) Au( 8)-Rh-A~(4)…”

Section: P-{1h}mentioning

confidence: 99%

Synthesis of heteronuclear gold–rhodium cluster compounds and structural characterisation of [Rh(CNC₈H₉)₃(AuPPh₃)₅]²⁺, [Rh(CNC₈H₉)₂(AuPPh₃)₆(AuCl)₂]⁺and [Rh(CO)₂(AuPPh₃)₇]²⁺

Bott¹,

Fleischer²,

Leach³

et al. 1991

J. Chem. Soc., Dalton Trans.

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Hetero‐metallic clusters. Synthesis and characterization of [PtAu₈ (PPh₃)₈] (NO₃)₂ and [HPtAu₇(PPh₃)₈](NO₃)₂

Cited by 36 publications

References 3 publications

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

Synthesis of heteronuclear gold–rhodium cluster compounds and structural characterisation of [Rh(CNC₈H₉)₃(AuPPh₃)₅]²⁺, [Rh(CNC₈H₉)₂(AuPPh₃)₆(AuCl)₂]⁺and [Rh(CO)₂(AuPPh₃)₇]²⁺

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Hetero‐metallic clusters. Synthesis and characterization of [PtAu8 (PPh3)8] (NO3)2 and [HPtAu7(PPh3)8](NO3)2

Cited by 36 publications

References 3 publications

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au8Hgx(PPh3)8]n+ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au8Hgx(PPh3)8]n+ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

Synthesis of heteronuclear gold–rhodium cluster compounds and structural characterisation of [Rh(CNC8H9)3(AuPPh3)5]2+, [Rh(CNC8H9)2(AuPPh3)6(AuCl)2]+and [Rh(CO)2(AuPPh3)7]2+

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Hetero‐metallic clusters. Synthesis and characterization of [PtAu₈ (PPh₃)₈] (NO₃)₂ and [HPtAu₇(PPh₃)₈](NO₃)₂

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Synthesis of heteronuclear gold–rhodium cluster compounds and structural characterisation of [Rh(CNC₈H₉)₃(AuPPh₃)₅]²⁺, [Rh(CNC₈H₉)₂(AuPPh₃)₆(AuCl)₂]⁺and [Rh(CO)₂(AuPPh₃)₇]²⁺