Ein Pt<sub>2</sub>AgH<sub>2</sub>‐Komplex

Albinati, Alberto; Demartin, Francesco; Venanzi, L. M.; Wolfer, Martin K.

doi:10.1002/ange.19881000409

Angewandte Chemie

1988

DOI: 10.1002/ange.19881000409

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Ein Pt₂AgH₂‐Komplex

Alberto Albinati

Francesco Demartin

L. M. Venanzi

et al.

Abstract: Ein Ag(PtH)2‐Spirocyclus ist das Kernstück des Komplexes 1, der bei der Zugabe von Ag[CF3SO3] zu zwei Äquivalenten trans‐[PtH(C6Cl5)(PEt3)2] in Ether entsteht. Die Pt‐Ag‐Abstände und Pt‐H‐Ag‐Winkel sind relativ klein (2.791(1) Å bzw. 107(2)°). Das zentrale Ag‐Atom kann als linear oder als pseudo‐tetraedrisch koordiniert betrachtet werden.

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“…As shown by 1 H and Hydrogen atoms are common ligands in transition metal chemistry [1] and can be bound to the cluster framework in a variety of ways. [2] Beside the most common terminal, bridging, and face-capping modes, [3] they can also occupy an interestitial coordination mode site, with up to six Hmetal interactions. [4,5] The hydride ligands in many clusters are abstracted from the solvent in which the cluster is prepared.…”

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Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

et al. 2003

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The carbonyl hydride cluster Ir4H8(CO)4(PPh3)4 (1) has been formed in high yield and purity by heating a mixture of Ir4(CO)12 and PPh3 in toluene at 90 °C under hydrogen at atmospheric pressure. The product has been characterised by microanalysis, spectroscopy (IR, 1H and 31P NMR) and X‐ray diffraction. In the solid state one hydrogen, one CO and one triphenylphosphane ligand are terminally bonded to each iridium atom, whereas four hydride ligands are bridging. All the hydrogen atoms were directly located by X‐ray analysis at an average H−Ir distance of 1.55 Å (for the terminal H) and 1.75 Å (for the μ‐H). As shown by 1H and 31P NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

et al. 2003

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ChemInform Abstract: A Pt2AgH2 Complex.

Albinati

Demartin

Venanzi³

et al. 1988

ChemInform

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Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

et al. 2013

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Keywords: Metal-metal interactions / P ligands / Palladium / Platinum / Structure elucidationThe reactions of [Ag(OClO 3 )(PPh 3 )] F 5 )(tht)] (M = Pt, Pd; hq = 8-hydroxyquinolinate, bq = benzoquinolinate, pic = picolinate, tht = tetrahydrothiophene) afford the corresponding neutral adducts [(C 6 F 5 ) 2 Pt-(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(bq)] (M = Pt, 1; Pd, 2), [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(hq)] (M = Pt, 3; Pd, 4) [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 -(μ-AgPPh 3 )Pt(C 6 F 5 )(tht)] (5) and [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 M(pic-AgPPh 3 )] (M = Pt, 6; Pd, 7) as yellow solids. The XRD structures of 1-5, in which a [AgPPh 3 ] + moiety bridges the metal Eur. 1679centres, were confirmed in solution at low temperature. At room temperature, a dynamic process for the [AgPPh 3 ] + moiety, which passes from the top to the bottom part of the molecules 1-5, was ascertained. For 6 and 7, the XRD analyses revealed structures in which the [AgPPh 3 ] + moiety is linked to the picolinate oxygen atom bonded to the M centre; however, although such a structure was confirmed in solution for the Pt-Pd species 7, the stable form of the Pt-Pt species 6 in solution is that with the [AgPPh 3 ] + moiety bridging the metal centres.www.eurjic.org FULL PAPER Scheme 1. num(III) (Scheme 1, type F) and the consequent formation of metallic silver. [38,[42][43][44] Finally, an example has been reported in which the L-LЈ ligand of [Ag 2 {Pt 2 (μ-PPh 2 ) 2 -(C 6 F 5 ) 2 (acac)} 2 ] (acac = acetylacetonate) acts as donor towards the silver atom (Scheme 1, type G and H). [36] In our experience, the results obtained so far in these types of reactions indicate that it is impossible to predict the behaviour of a particular complex towards Ag I .Recently, we have reported the reactions of I 2 with [NBu 4 ][(C 6 F 5 ) 2 Pt II (μ-PPh 2 ) 2 M II (C ∧ N)] [45] and [NBu 4 ]-[(C 6 F 5 ) 2 Pt II (μ-PPh 2 ) 2 M II (O ∧ N)] [46] [M = Pt, Pd; C ∧ N = benzoquinolinate (bq); O ∧ N = 8-hydroxyquinolinate (hq), picolinate (pic)], which contain dinuclear asymmetric anionic complexes and a chelate ligand. In all cases, the addition of molecular I 2 to the complexes resulted in oxidation of the metal centre and the formation of M II -M IV intermediates, which evolved through a PPh 2 /C ∧ N or PPh 2 / O ∧ N reductive coupling with the formation of new M II -M II compounds.In this paper, we report the results obtained in the reactions of anionic complexes of platinum(II) and palladium(II) containing benzoquinolinate, 8-hydroxyquinolinate, tetrahydrothiophene (tht) and picolinate ligands with [AgPPh 3 (OClO 3 )]; these reactions were performed to establish the type of complex (A-H, Scheme 1) obtained when the different dinuclear phosphanido platinum or palladium fragments are reacted with Ag I salts. Results Synthesis and Solid-State StructuresThe addition of [Ag(OClO 3 )(PPh 3 )] to CH 2 Cl 2 solutions of [NBu 4 ][(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 M(hq)], [46] [NBu 4 ][(C 6 F 5 ) 2 -Eur.

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Ein Pt₂AgH₂‐Komplex

Cited by 3 publications

References 10 publications

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

ChemInform Abstract: A Pt2AgH2 Complex.

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

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Ein Pt2AgH2‐Komplex

Cited by 3 publications

References 10 publications

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir4H4(μ‐H)4(CO)4(PPh3)4

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir4H4(μ‐H)4(CO)4(PPh3)4

ChemInform Abstract: A Pt2AgH2 Complex.

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

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Product

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Ein Pt₂AgH₂‐Komplex

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄