Synthesis and characterization of cationic gold-iridium clusters. Structure of [IrAu2(H)(PPh3)4NO3]BF4

Casalnuovo, A. L.; Laska, T.; Nilsson, P. V.; Olofson, Jeffrey M.; Pignolet, L. H.

doi:10.1021/ic00196a013

Cited by 17 publications

(3 citation statements)

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“…Similar metal-gold separations have been found in other heterometallic complexes having bridging hydrides, e.g., 2.697 (1) and 2.673 (1) in [IrAu2(H)(PPh3)4(N03) ] BF4. 33 The Ir-P bond distances are unequal due to the different trans influence of the various coligands; thus, the longest value [2.354…”

Section: __á_mentioning

confidence: 99%

“…Chaudret et al have recently reported the preparation and characterization of the NMR static, neutral complex [ (ij-C5Mes){(C6H 1i )3P}Ru^-H){ Au(PPh3}2] (6), but no X-ray data are available (Chart I).26c Pignolet et al reported the X-ray structure of [IrAu2(H)(PPh3)4(N03)]BF4 (7) without being able to precisely determine the bonding mode of the hydride ligand. 33 In fact, while NMR measurements were diagnostic for a terminal hydride stereochemistry, potential energy calculations based on the X-ray coordinates of the non-hydrogen atoms indicated that a bridging hydride may be nicely accommodated over one of the two iridium-gold bonds. Unfortunately, the hydride ligand could not be located by X-ray methods.…”

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confidence: 99%

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Mixed iridium-gold hydrides as model compounds for elucidating the interconversion between classical and nonclassical polyhydrides

Bianchini¹,

Meli²,

Peruzzini³

et al. 1992

Inorg. Chem.

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The reaction of [(triphos)Ir(H)(C2H4)] (1) or [(triphos)Ir(H)2(C2H5)] ( 2) with [Au(THF)(PPh3)]PF6 under ethylene produces the monogold adduct [(triphos)Ir(H)(C2H4){Au( PPh3)}]PF6 (3) which exhibits a terminal hydride ligand in the solid state, but contains a bridging hydride in solution [triphos = CH3C(CH2PPh2)3], Addition of 1 equiv of [AuCl(PPh3)] to 3 yields the iridium-digold adduct [(triphos)(Cl)Ir(#t-H){Au2(PPh3)2}]PF6 (4). Complex 4 and its arsino analogue [(triphos)(Cl)Ir(g-H){Au2(AsPh3)2}]PF6 (5) can be prepared straightforwardly by reacting 1

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Section: __á_mentioning

confidence: 99%

Section: __á_mentioning

confidence: 99%

Mixed iridium-gold hydrides as model compounds for elucidating the interconversion between classical and nonclassical polyhydrides

Bianchini¹,

Meli²,

Peruzzini³

et al. 1992

Inorg. Chem.

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“…In striking contrast, neutral or cationic gold(I) fragments form stable bridging compounds with a plethora of other transition-metal hydride complexes spanning the whole d block, including Nb, Mo, W, Cr, Mn, Re, , Ru, , Os, Ir, − Rh, Pt, , Cu . In light of the Au + /H + isolobal relationship, the stabilization of such bimetallic structures has been generally ascribed to the occurrence of donor–acceptor interactions, or 3-center-2-electron (3c–2e) bonding, with different implied degrees of metal–metal bonding contribution.…”

Section: Introductionmentioning

confidence: 99%

Exploring Ligand Effects on Structure, Bonding, and Photolytic Hydride Transfer of Cationic Gold(I) Bridging Hydride Complexes of Molybdocene and Tungstenocene

Landrini,

Patel,

Tyrrell-Thrower

et al. 2024

Inorg. Chem.

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A diverse family of heterobimetallic bridging hydride adducts of the type [LAu(μ-H)2MCp2][X] (L = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, IPr; 1,3-bis(1-adamantyl)imidazole-2-ylidene, IAd; 1,3-bis(2,6-di-iso-propylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene, DippDAC; triphenylphosphine, PPh3; 2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl, tBuXPhos; X = SbF6 –, BF4 – or TfO–) was synthesized by reacting group VI metallocene dihydrides Cp2MH2 (Cp = cyclopentadienyl anion; M = Mo, W) with cationic gold(I) complexes [LAu(NCMe)][X]. Trimetallic [L′Au2(μ-H)2WCp2][X]2 and tetrametallic [L′Au2{(μ-H)2WCp2}2] [X]2 complexes (L′ = rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene or bis(diphenylphosphinomethane)) were obtained by reacting digold [L′{Au(NCMe)}2][X]2 with Cp2WH2 in a 1:1 and a 1:2 stoichiometry. Accessing such a broad structural diversity allowed us to pinpoint roles played by the ancillary ligands and group VI metals on the bonding properties of this family of bridging hydrides. In particular, a clear effect of the ligand on the interaction energy and electronic structure was observed, with important implications on photolytic reactivity. UV or visible light irradiation, indeed, leads to the selective cleavage of the heterobimetallic Au(μ-H)2M arrangement and formation of molecular gold hydrides. The photolysis was found to be chromoselective (wavelength-dependent), which can be ascribed to different charge redistributions upon excitation to the first (Kasha’s reactivity) and higher (anti-Kasha’s reactivity) excited states.

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Mixed‐Metal‐Gold Phosphine Cluster Compounds

Mueting¹,

Alexander²,

Boyle³

et al. 1992

Inorganic Syntheses

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Synthesis and characterization of cationic gold-iridium clusters. Structure of [IrAu2(H)(PPh3)4NO3]BF4

Cited by 17 publications

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Mixed iridium-gold hydrides as model compounds for elucidating the interconversion between classical and nonclassical polyhydrides

Mixed iridium-gold hydrides as model compounds for elucidating the interconversion between classical and nonclassical polyhydrides

Exploring Ligand Effects on Structure, Bonding, and Photolytic Hydride Transfer of Cationic Gold(I) Bridging Hydride Complexes of Molybdocene and Tungstenocene

Mixed‐Metal‐Gold Phosphine Cluster Compounds

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