On the Borderline between <i>cis</i> and <i>trans</i> in Organometallic(Phosphane)platinum(<scp>II</scp>) Complexes

Gudat, Dietrich; Jain, Vimal K.; Klein, Axel; Schurr, Thilo; Záliš, Stanislav

doi:10.1002/ejic.200500251

Cited by 21 publications

(15 citation statements)

References 25 publications

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“…The J PtC value (770 Hz) is comparable with that of cis-[PtPh 2 (PEt 3 ) 2 ] (879 Hz). 16 27 The second Si−C bond formation from the μ-SiPh 2 and μ-CZCZSiPh 2 ligands and subsequent ring contraction by the silyl migration afford a disilaplatinacyclopentene intermediate (B) with a silylene-bridged diplatinum moiety. It is contrasted with the reaction of [{Pt(PMe 3 )} 3 (μ-GePh 2 ) 3 ], which also undergoes insertion of the alkyne into the Pt−Ge bond but produces the triangular Pt 3 complexes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si–Pt Bond

et al. 2015

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Triangular triplatinum(0) complexes with bridging diarylsilylene ligands, [{Pt(PMe 3 )} 3 (μ-SiAr 2 ) 3 ] (1: Ar = Ph, 2: Ar = C 6 H 4 F-4), reacted with dimethyl acetylenedicarboxylate to afford new Pt 3 complexes. The equimolar reaction of complex 1 produced a linear triplatinum complex with μ 2 -diphenylsilylene and μ 3 -phenyl(vinylene)silylene ligands. The latter ligand was formed via migration of a Ph group of the bis(diphenylsilyl)ethylene ligand. The reaction of 2 with the alkyne in a 1:3 molar ratio yielded the product having a disilaplatinacyclic moiety and a Pt center with the donorstabilized silylene ligand, and they were separated by the coordinated alkyne molecule. A common intermediate having a disilaplatinacyclopentene group was converted into the respective triplatinum complexes, depending on the substituents of the silylene ligand. ■ INTRODUCTIONMultinuclear complexes of low-valent late transition metals are mostly stabilized by bridging inert and electron-withdrawing ligands, such as μ-CO and μ-CNR. 1 The bridging silylene ligands (μ-SiR 2 ), having electron-donating nature, bind two transition metals and form stable dinuclear complexes. 2 The multinuclear late transition metal complexes with the bridging Si ligands were uncommon until recently. 3 Our group 4 and Braddock-Wilking's group 5 reported triangular triplatinum(0) complexes with bridging silylene ligands, formulated as [{Pt(PR′ 3 )} 3 (μ-SiR 2 ) 3 ]. These complexes are stable up to 100°C despite mismatched coordination of the d 10 transition metal centers to the electrondonating ligands. An analogous complex with bridging germylene ligands contains a stable triangular Pt 3 framework, which is kept after protonation and insertion of alkyne into a Pt−Ge bond. 6 A triplatinum complex with bridging carbonyl ligand, [{Pt(PR 3 )} 3 (μ-CO) 3 ], reacts with alkyne to afford a diplatinum−alkyne complex, accompanied by elimination of the Pt(PR 3 )(CO) fragment. 7 Recently, tetranuclear Pd complexes, with more flexibility than the cyclic Pt 3 complexes, were reported to undergo their skeletal rearrangement. Linear tetrapalladium complexes in a sandwich framework underwent reversible change in alignment of the Pd metals upon chemical oxidation and reduction. 8 We found structural change of the planar Pd 4 Ge 3 complex [Pd{Pd(dmpe)} 3 (μ-GePh 2 ) 3 ] (dmpe = 1,2-bis-(dimethylphosphino)ethane) caused by addition of thiol, giving a linear hexapalladium complex, although the reaction occurred irreversibly. 9 Thus, the cyclic triplatinum(0) complexes tend not to change the Pt 3 core in most reactions reported so far. In this paper, we report rearrangement reactions of the silylene-bridged triplatinum(0) complexes induced by insertion of alkyne into a Si−Pt bond and its pathway involving isomerization of the initial product. ■ RESULTS AND DISCUSSIONThe triplatinum(0) complexes with bridging diarylsilylene ligands, [{Pt(PMe 3 )} 3 (μ-SiAr 2 ) 3 ] (1: Ar = Ph, 2: Ar = C 6 H 4 F-4), were prepared by an equimolar reaction of H 2 SiAr 2 with [Pt(PMe 3 ) 4 ...

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Section: ■ Results and Discussionmentioning

confidence: 99%

Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si–Pt Bond

et al. 2015

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“…Thus, the reaction of trans-PtCl 2 L 2 gives a mixture of the cis and trans dihydrocarbyl species. This behaviour reflects the general tendency in platinum(II) chemistry for hydrocarbyl ligands to appear cis, unless for steric reasons [15,16]. The reactions were in general very facile giving the transmetallated species in high yield.…”

Section: Methodsmentioning

confidence: 81%

Transmetallation Reactions Involving Group 10 Metals

Wendt

2007

COC

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“…The bulky ligands generally confer trans configuration, whereas the strong σ -donor ligands impose cis conformation around the metal center due to the trans influence. 45 and 2 [1.468(2) Å] are nearly identical. The exocyclic and endocyclic P-N bond distances in 7 are shorter than that found in 2, but follow the same trend.…”

Section: -C 3 H 5 )] 2 In Dichloromethane Gave [(η 3 -C 3 H 5 )Pdclmentioning

confidence: 82%

A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

2015

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The hydrolysis of cis-{ClP(μ-N t Bu) 2 P(NH t Bu)} (1) produced a mixed P III /P V derivative of cyclodiphosphazane, cis-{( t BuNH)P(μ-N t Bu) 2 P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-dichloromethane afforded corresponding mononuclear complexes, [(η 3 -C 3 H 5 )PdCl{( t BuNH)P(μ-N t Bu) 2 P(O)H}] (4) and [((η 6 -p-cymene)RuCl 2 ){( t BuNH)P(μ-N t Bu) 2 P(O)H}] (5). The treatment of 2 with M(COD)Cl 2 (M = Pd and Pt) in dichloromethane at room temperature gave [MCl 2 {( t BuNH)P(μ-N t Bu) 2 P(O)H} 2 ] (6 M = Pd; 7 M = Pt) in good yield.Owing to the cis/trans isomerisation of the cyclodiphosphazane rings, the complexes 6 and 7 exist as a mixture of two isomers. Various NMR spectroscopic techniques were employed for structural elucidation. The molecular structures of 5 and 7 were established by single crystal X-ray crystallographic studies.

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On the Borderline between cis and trans in Organometallic(Phosphane)platinum(II) Complexes

Cited by 21 publications

References 25 publications

Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si–Pt Bond

Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si–Pt Bond

Transmetallation Reactions Involving Group 10 Metals

A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

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