Platinum(II) 1,5-COD Oxo Complexes

Shan, Hui; James, and Alan J.; Sharp, Paul R.

doi:10.1021/ic980818+

Cited by 28 publications

(24 citation statements)

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“…[21] To the best of our knowledge, the only complex featuring an unsupported d 10 -d 10 interaction (type D) between platinum and a coinage-group metal was reported by Sharp et al in 1998. [22] However, no signs of an insertion reaction were detected at that time.…”

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confidence: 93%

Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

et al. 2012

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Insertion of transition-metal (TM) complexes into elementhalogen bonds is one of the basic concepts in TM chemistry. The most common examples are found for main-group species such as alkyl [1][2][3] and boryl halides. [4][5][6][7] Here, the insertion proceeds with oxidation of the TM and thus constitutes an oxidative addition (OA) process, which is a crucial step in TM-mediated catalysis. Another possibility, albeit much less common, is the insertion of a main-group metal such as tin into TM-halogen bonds, which does not affect the oxidation state of the TM. [8][9][10][11] In the present work we focus on the combination of these two reaction patterns, that is, the insertion of a TM into a TM-halogen bond; this constitutes a versatile route to heterodinuclear TM complexes containing platinum and a coinage metal.There have been numerous investigations into the bonding properties of homo-and heterodinuclear transition-metal complexes. Among the earliest examples were homodinuclear complexes consisting of d 8 -d 8 as well as d 10 -d 10 systems (type B, Figure 1). [12][13][14][15] However, the combination of plati-num and gold is exclusively found in mixed-valence systems, such as d 8 -d 10 (type A) and d 7 -d 9 ; [16][17][18][19] in contrast, the route presented herein leads to heterodinuclear d 10 -d 10 complexes. In addition, the most striking feature of nearly all known compounds of this type is the chelating ligand forcing the two transition metals to interact. Again this stands in stark contrast to the compounds presented in this work that contain unsupported TM-TM bonds without a bridging ligand.While unsupported bonds are relatively uncommon, [20] a few examples of complexes having d 8 -d 10 interactions should be mentioned (type C). [21] To the best of our knowledge, the only complex featuring an unsupported d 10 -d 10 interaction (type D) between platinum and a coinage-group metal was reported by Sharp et al. in 1998. [22] However, no signs of an insertion reaction were detected at that time.In contrast, in our synthetic approach we use the wellestablished transition-metal Lewis base [(Cy 3 P) 2 Pt] (1) and the gold complex [(Cy 3 P)AuCl] (2). We describe the unprecedented reversible insertion of the Lewis basic platinum fragment into a coinage-metal-halogen bond. The insertion products were investigated by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. In addition, we present a possible mechanism for the insertion reaction supported by density functional calculations.The reaction of the sterically and electronically unsaturated platinum compound [(Cy 3 P) 2 Pt] (1) with an equimolar amount of [(Cy 3 P)AuCl] (2) leads instantly to an equilibrium of the two starting materials with a new complex 3, as indicated by 31 P{ 1 H} NMR spectroscopic data. The resonances of 1 (d = 62.2 ppm), flanked by 195 Pt satellites (J = 4155 Hz), and 2 (d = 53.1 ppm) are accompanied by the resonances of 3 at d = 42.7 ppm (J = 3157 Hz) and d = 38.2 ppm (J = 1295 Hz). The appearance of 195 Pt satellites in bo...

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Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

et al. 2012

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“…[16] We have also reported on chalcogenide-centered complexes with gold atoms in different oxidation states, [17] but all attempts to prepare heteronuclear derivatives have led to a mixture of complexes. As far as we are aware only the mixed-metal chalcogenide-centered complexes [{OA C H T U N G T R E N N U N G (Au-A C H T U N G T R E N N U N G PPh 3 ) 2 (RhA C H T U N G T R E N N U N G {dien})} 2 ]A C H T U N G T R E N N U N G (BF 4 ) 2 (dien = 1,5-cyclooctadiene (cod), norbornadiene (nbd)), [19] [{OA C H T U N G T R E N N U N G (AuPPh 3 )(PtA C H T U N G T R E N N U N G {cod})} 2 ]A C H T U N G T R E N N U N G (BF 4 ) 2 , [20] [{OA C H T U N G T R E N N U N G (AuPPh 3 )PdA C H T U N G T R E N N U N G (tBu 2 bipy)} 2 ] 2 + , [21] [ 3 , [22] [Au 4 A C H T U N G T R E N N U N G (SeInCl 3 ) 2 A C H T U N G T R E N N U N G {Ph 2 PA C H T U N G T R E N N U N G (CH 2 ) 5 PPh 2 } 2 ], [23] and [Au 8 Se 4 -A C H T U N G T R E N N U N G InA C H T U N G T R E N N U N G {Ph 2 PA C H T U N G T R E N N U N G (CH 2 ) 2 PPh 2 } 4 ]A C H T U N G T R E N N U N G (InCl 4 ) 3 , [23] have been reported. A strategy to prepare these chalcogenide-centered heteronuclear derivatives involves the use of heterofunctional ligands such as the phosphines PPh 2 py or PPh 2 CH 2 CH 2 py.…”

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confidence: 99%

Highly Luminescent Gold(I)–Silver(I) and Gold(I)–Copper(I) Chalcogenide Clusters

Crespo

Gimeno

Laguna

et al. 2006

Chemistry A European J

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The reactions of [AuClL] with Ag2O, where L represents the heterofunctional ligands PPh2py and PPh2CH2CH2py, give the trigoldoxonium complexes [O(AuL)3]BF4. Treatment of these compounds with thio‐ or selenourea affords the triply bridging sulfide or selenide derivatives [E(AuL)3]BF4 (E=S, Se). These trinuclear species react with Ag(OTf) or [Cu(NCMe)4]PF6 to give different results, depending on the phosphine and the metal. The reactions of [E(AuPPh2py)3]BF4 with silver or copper salts give [E(AuPPh2py)3M]2+ (E=O, S, Se; M=Ag, Cu) clusters that are highly luminescent. The silver complexes consist of tetrahedral Au3Ag clusters further bonded to another unit through aurophilic interactions, whereas in the copper species two coordination isomers with different metallophilic interactions were found. The first is analogous to the silver complexes and in the second, two [S(AuPPh2py)3]+ units bridge two copper atoms through one pyridine group in each unit. The reactions of [E(AuPPh2CH2CH2py)3]BF4 with silver and copper salts give complexes with [E(AuPPh2CH2CH2py)3M]2+ stoichiometry (E=O, S, Se; M=Ag, Cu) with the metal bonded to the three nitrogen atoms in the absence of Au⋅⋅⋅M interactions. The luminescence of these clusters has been studied by varying the chalcogenide, the heterofunctional ligand, and the metal.

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“…Zu den frühesten Beispielen zählen homodinukleare Spezies von d 8 [20] jedoch sollten einige Beispiele mit d 8 -d 10 -Wechselwirkungen (C) erwähnt werden. [21] Unseres Wissens wurde der einzige Komplex mit d 10 [22] jedoch ohne Hinweis auf eine Insertionsreaktion.…”

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“…Solche Bindungen sind zwar relativ selten, [20] jedoch sollten einige Beispiele mit d 8 -d 10 -Wechselwirkungen (C) erwähnt werden. [21] Unseres Wissens wurde der einzige Komplex mit d 10 -d 10 -Wechselwirkung (D) ohne Brückenligand zwischen Platin und einem Münzmetall 1998 von Sharp et al beschrieben, [22] jedoch ohne Hinweis auf eine Insertionsreaktion.Im Unterschied dazu gehen wir bei unserem Syntheseansatz von der wohlbekannten ÜM-Lewis-Base [(Cy 3 P) 2 Pt] (1) und dem Goldkomplex [(Cy 3 P)AuCl] (2) aus und beschreiben eine präzedenzlose, reversible Insertion des Lewisbasischen Platinfragments in Münzmetall-Halogen-Bindungen. Die Insertionsprodukte wurden durch Multikern-NMR-Spektroskopie und Einkristallrçntgendiffraktometrie charakterisiert.…”

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Reversible Insertion von Platin in Münzmetall‐Halogen‐Bindungen

et al. 2012

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M & M: Durch die reversible Insertion eines Platinkomplexes in Münzmetall‐Halogen‐Bindungen wurde eine Reihe von allein aus Metallen bestehenden Lewis‐Paaren erhalten, die also nicht durch zusätzliche Brücken stabilisiert sind. In den Lewis‐Paaren koordiniert das Lewis‐basische Platin(0)‐Fragment an kationische Kupfer‐, Silber‐ und Gold‐Lewis‐Säuren (siehe Schema; M=Cu, Ag, Au; Cy=Cyclohexyl).

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Platinum(II) 1,5-COD Oxo Complexes

Cited by 28 publications

References 26 publications

Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds

Highly Luminescent Gold(I)–Silver(I) and Gold(I)–Copper(I) Chalcogenide Clusters

Reversible Insertion von Platin in Münzmetall‐Halogen‐Bindungen

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