Reaction between Dithiirane 1-Oxides and a Platinum(0) Complex

Ishii, Akihiko; Saito, Masashi; Murata, Masami; Nakayama, Juzo

doi:10.1002/1099-0690(200203)2002:6<979::aid-ejoc979>3.0.co;2-2

Cited by 38 publications

(21 citation statements)

References 23 publications

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“…Of those that are known only the mixed thiolato±sulfenato complexes have been obtained by oxidative addition reactions and examples of this seem to be limited to reactions of cyclic thiosulfinates with Pt 0 precursors [14±20] and dithiirane 1oxides. [21] Thiolato±sulfenato (-SÀMÀS(=O)-) complexes have also been prepared through the mono-oxidation of dithiolate complexes of which the diiron compounds [{(OC) 3 -Fe} 2 SCH 2 CH 2 S(=O)] and [{(OC) 3 Fe} 2 SC 6 H 10 S(=O)] containing bridging 1,2-ethanesulfenatothiolato and 1,2-cyclohexylsulfenatothiolato ligands are illustrative examples. [22,23] This preparative method has also been utilised by Darensbourg and co-workers in the preparation a series of thiolato±sulfenato, disulfenato, thiolato±sulfinato, sulfenato±sulfinato and disulfinato complexes of nickel(ii) and palladium(ii) from bis(2-mercaptoethyl)-1,5-diazacyclooctane-M II (M = Ni, Pd) and N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane-Ni II .…”

Section: Introductionmentioning

confidence: 99%

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Aucott

Milton

Robertson

et al. 2004

Chemistry A European J

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Platinum bisphosphine complexes bearing dichalcogen-derivatised naphthalene, acenaphthene or phenanthrene ligands have been prepared by either oxidative addition to zero-valent platinum species or from [PtCl(2)(PPhR(2))] (R=Ph or Me) and the disodium or dilithium salts of the parent disulfur, diselenide or mixed S/Se species. The parent naphthalene, acenaphthene and phenanthrene chalcogen compounds were treated with either [Pt(PPh(3))(4)] or [Pt(C(2)H(4))(PMe(3))(2)] (prepared in situ from [PtCl(2)(PMe(3))(2)], ethene and sodium naphthalide or super hydride [LiBEt(3)H]) to give the appropriate platinum(II) species. The dilithium salts of 1,8-E(2)-naphthalene (E=S or Se) prepared in situ by reduction of the E-E bond with [LiBEt(3)H] were treated with [PtCl(2)(PPh(3))(2)] to give [Pt(1,8-E(2)-nap)(PPh(3))(2)]. The tetraoxides [Pt(1,8-(S(O)(2))(2)-nap)(PR(3))(2)] (PR(3)=PPh(3) or PMe(2)Ph) were prepared in a similar metathetical manner from the appropriate [PtCl(2)(PR(3))] complexes and the disodium salt of naphthalene 1,8-disulfinic acid (1,8-(S(O)ONa)(2)-nap). The X-ray structures of selected examples reveal bidentate coordination with the naphthalene-E(2) unit hinged (111-137 degrees) with respect to the coordination plane. The naphthalene ring suffers significant distortion from planarity.

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Section: Introductionmentioning

confidence: 99%

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Aucott

Milton

Robertson

et al. 2004

Chemistry A European J

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“…The molar ratio was obtained based on the 31 P NMR integral ratio. The S ‐oxides of 12 are considered to be formed by reactions of dithiirane 1‐oxides 15 with 4 31. The binuclear platinum complex 16 could not isolated in this experiment because it was not eluted from the silica‐gel column.…”

Section: Methodsmentioning

confidence: 96%

“…We have been studying the synthesis and reactivities of cyclic polysulfides, and have reported on the chemistry of tetrathiolane 2,3‐dioxide ( 5 ),22,23 pentathiane 3‐oxide ( 6 ),24,25 and S 8 O,26 all of which act as S 2 O transfer reagents 27−30. Recently we also reported the reaction of dithiirane 1‐oxides 7 with 4 31. Here, we report the reaction of 5 , 6 , and tetrathiolane 2‐oxide ( 8 )23 with 4 , where an S 2 O transfer took place giving rise to [(Ph 3 P) 2 Pt(S 2 O)] which further reacted with 4 to yield the binuclear platinum complex [(Ph 3 P) 4 Pt 2 (μ‐S)(μ‐SO)].…”

Section: Methodsmentioning

confidence: 99%

“…), [(Ph 3 P) 2 Pt{(1‐Ad)( t Bu)C=S}] ( 13 ; 0.31 molar equiv. ),31 and (1‐Ad)( t Bu)C=S ( 14 ; 0.47 molar equiv.) [Equation (1 )]. …”

Section: Methodsmentioning

confidence: 99%

“…The solution turned immediately from colorless to deep yellow and was stirred for 10 min at −20 °C. Removal of the solvent under reduced pressure gave an orange residue, the 31 P NMR integral ratio of which indicated the formation of the thioketone complex 13 , [(PPh 3 ) 4 Pt 2 ‐(μ‐S)(μ‐SO)] ( 16 ), the S 2 O complex 10 , and the S ‐oxides of 12 31 in the molar ratio of 26:13:29:32, along with Ph 3 P=O and Ph 3 P=S. The molar ratio was obtained based on the 31 P NMR integral ratio.…”

Section: Methodsmentioning

confidence: 99%

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Oxosulfido Complexes of Platinum — (Ph₃P)₂Pt(S₂O) and (Ph₃P)₄Pt₂(μ‐S)(μ‐SO) — Their Formation and Properties

et al. 2003

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Sind Überlegungen zur Zukunft relevant oder dienen sie nur der Zerstreuung? Regelmäßig werden wichtige Grundüberzeugungen aufgrund wissenschaftlicher Erkenntnisse verworfen, mit oft tiefgreifenden Folgen für die Gesellschaft. Falsche Annahmen lassen sich im Nachhinein leicht ausmachen, aber lassen sie sich auch in der Gegenwart erkennen, und lassen sich aus der Erkenntnis Schlussfolgerungen für die Zukunft ziehen? Dieser Essay diskutiert gesellschaftlich akzeptierte Annahmen und das Potenzial der Naturwissenschaften, sie zu widerlegen.

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Reactions of a Ditriptycyl‐Substituted Selenoseleninate and Related Compounds with a Platinum(0) Complex: Formation of Selenaplatinacycle and Hydrido Selenolato Platinum(II) Complexes

et al. 2008

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Dedicated to Professor Renji Okazaki on the occasion of his 70th birthdayOxidative additions of cyclic and acyclic disulfides and their oxides to platinum(0) complexes are a topic of recent research. [1][2][3] However, analogous reactions of selenium compounds are limited to diselenides. [3,4] For example, in the diselenation of terminal acetylenes with diselenides in the presence of palladium(0) and platinum(0) complexes, [5,6] diselenolato complexes have been proposed as the intermediates. As far as we know, there are no reports on analogous reactions for oxides of diselenides such as selenoseleninates (RSe(O)SeR), a major reason for which must be that only few isolable selenoseleninates are known. [7, 8] It is important to investigate their reactivity toward low-valent transition-metal complexes and the nature of the resulting selenium metal complexes in relation to the corresponding chemistry of sulfur.Previously we reported the preparation of selenoseleninate 1 by dehydration of selenenic acid 2 or oxidation of diselenide 3 (Scheme 1).[7] Selenoseleninates 1 and 4 are the only such species isolable under ambient conditions. Herein we report the reactions of 1 and its related compounds with a platinum(0) complex. We unexpectedly observed the formation of a five-membered selenaplatinacycle by intramolecular C À H activation.[9] The chemistry of chalcogenametallacycles is also interesting in relation to the mechanistic study of homogeneous hydrodesulfurization of crude oil distillates. The formation of thiaplatinacycles 5[10] and selenametallacycles 6[11] by insertion of low-valent transition metals into C À S and C À Se bonds of the thiophene and selenophene derivatives, respectively, has been revealed.We first examined the reaction of selenoseleninate 1 with [Pt(PPh 3 ) 2 (h 2 -C 2 H 4 )] (7) in the expectation of obtaining the corresponding selenenato selenolato platinum(II) complex [Pt(SeTrip){Se(O)Trip}(PPh 3 ) 2 ]. However, when 1 was treated with 1.1 molar equivalents of 7 in toluene at room temperature, we obtained an unexpected compound (8, 0.72 molar equiv) together with diselenide 3 (0.30 molar equiv, 30 %) [Eq. (1)]. In the 31 P NMR spectrum of the compound, two doublets with accompanying satellite signals from the 195 Pt isotope are observed at d = 22.7 (d, 2 J(P,P) = 20.4 Hz, 1 J(Pt,P) = 1833 Hz) and 25.3 ppm (d, 2 J(P,P) = 20.4 Hz, 1 J-(Pt,P) = 3276 Hz). In the 1 H NMR spectrum, a characteristic signal appears at d = 5.81-5.88 ppm (m, 1 H). The structure was finally shown by X-ray crystallography to be selenaplatinacycle 8 (Figure 1). The signal in the 31 P NMR spectrum at d = 25.3 ppm with 1 J(Pt,P) = 3276 Hz was assigned to the Scheme 1. Formation of selenoseleninates from selenenic acids and diselenides.

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Reaction between Dithiirane 1-Oxides and a Platinum(0) Complex

Cited by 38 publications

References 23 publications

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Oxosulfido Complexes of Platinum — (Ph₃P)₂Pt(S₂O) and (Ph₃P)₄Pt₂(μ‐S)(μ‐SO) — Their Formation and Properties

Reactions of a Ditriptycyl‐Substituted Selenoseleninate and Related Compounds with a Platinum(0) Complex: Formation of Selenaplatinacycle and Hydrido Selenolato Platinum(II) Complexes

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Reaction between Dithiirane 1-Oxides and a Platinum(0) Complex

Cited by 38 publications

References 23 publications

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Platinum Complexes of Naphthalene‐1,8‐dichalcogen and Related Polyaromatic Hydrocarbon Ligands

Oxosulfido Complexes of Platinum — (Ph3P)2Pt(S2O) and (Ph3P)4Pt2(μ‐S)(μ‐SO) — Their Formation and Properties

Reactions of a Ditriptycyl‐Substituted Selenoseleninate and Related Compounds with a Platinum(0) Complex: Formation of Selenaplatinacycle and Hydrido Selenolato Platinum(II) Complexes

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Oxosulfido Complexes of Platinum — (Ph₃P)₂Pt(S₂O) and (Ph₃P)₄Pt₂(μ‐S)(μ‐SO) — Their Formation and Properties