Extending The Reaction Landscape of the {Pt(μ‐S)<sub>2</sub>Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

González-Duarte, Pilar; Lledós, Agustı́; Mas‐Ballesté, Rubén

doi:10.1002/ejic.200400422

Cited by 47 publications

(20 citation statements)

References 80 publications

(191 reference statements)

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“…[54] Concerning the terminal dppp ligands, they adopt a distorted chair conformation that compares very well with that usually found in dinuclear complexes enclosing different bridging ligands between two {(dppp)Pt II } fragments. [55] This is the first structurally characterized example of a dinuclear platinum compound resulting from the S-C activation of thiophene.…”

Section: Cationmentioning

confidence: 98%

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

et al. 2007

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[(dppp)2Pt2H3]ClO4 [I, dppp = Ph2P(CH2)3PPh2] was found to activate the C–S bond and to cause partial hydrogenation of thiophene. Thus, the reaction of I with neat thiophene (T) at reflux temperature yields [(dppp)Pt(SC4H4‐C,S)] (II) and [(dppp)2Pt2(μ‐SC4H5‐C,S)]ClO4 (III) at a 2:3 molar ratio. The same reaction in toluene or benzene solvent affords the same complexes II and III but in a 1:9 molar ratio. The concomitant formation of II and III was interpreted on the basis of theoretical calculations (DFT), which have provided a detailed insight into the reaction mechanism. Thus, the presence of T causes I to dissociate into [(dppp)PtH2] and [(dppp)PtH(C4H4S‐κS)], this process being a common step for the two ensuing reaction pathways. After dissociation, the activation of the thiophene C–S bond to yield II involves participation of [(dppp)PtH2] exclusively. However, the reaction leading to III requires the internal migration of the coordinated hydride to the thiophene ligand in [(dppp)PtH(C4H4S‐κS)] and the subsequent assistance of the {(dppp)Pt} fragment formed from [(dppp)PtH2] by hydrogen elimination. As a result of the involvement of [(dppp)PtH2] in the formation of both II and III, the two reaction pathways are competitive. The reactivity of II and III with various sources of hydride ligands and different protonic acids has also been examined. Thus, the reaction of II with HBF4 leads to the thiolate‐bridged dinuclear complex [(dppp)2Pt2(μ‐SC4H5)2](BF4)2 (IV). In the case of III the addition of HBF4 leads to [(dppp)2Pt2(μ‐SC4H6)](BF4)2 (V), which transforms into III by the addition of a base. The X‐ray structural characterization of the unprecedented complex V is reported here.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Cationmentioning

confidence: 98%

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

et al. 2007

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“…[10] Understanding the rich chemistry of [Pt 2 A C H T U N G T R E N N U N G (m-S) 2 A C H T U N G T R E N N U N G (P\P) 2 ] complexes has been the aim of our research for several years. [13] Now, taking advantage of the knowledge accumulated over this time, we have studied how [Pt 2 …”

Section: A C H T U N G T R E N N U N G (P\p) 2 ] [Ni 2 a C H T U N Gmentioning

confidence: 99%

Reaction Chemistry of Complexes Containing PtH, PtSH, or PtS Fragments: From Their Apparent Simplicity to the Maze of Reactions Underlying Their Interconversion

Novio

González-Duarte

Lledós

2007

Chemistry A European J

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The relevance of platinum in the reaction of thiophene and derivatives with homogeneous transition-metal complexes as models for hydrodesulfurization has led us to the study of the reaction chemistry of complexes containing Pt--H, Pt--SH, and Pt--S fragments. Exploration of the reactions triggered by addition of controlled amounts of Na2S or NaSH to [Pt2(H)2(mu-H)(dppp)2]ClO4 (1) has provided evidence of the formation of complexes [Pt2(mu-H)(mu-S)(dppp)2]ClO4 (2), [Pt(H)(SH)(dppp)] (3), [Pt2(mu-S)2(dppp)2] (4), [Pt2(mu-S)(dppp)2] (5) and [Pt(SH)2(dppp)], in which dppp denotes 1,3-bis(diphenylphosphanyl)propane. Consequently, complexes 1, 2, and 5 as well as the already reported 3, 4, and [Pt(SH)2(dppp)] have been obtained and fully characterized spectroscopically. Also the crystal structures of 1 and 2 have been solved. Complexes 1-5 constitute the main framework of the network of reactions that account for the evolution of 1 under various experimental conditions as shown in Scheme 1. Apparently, this network has complexes 2 and 4 as dead-ends. However, their reciprocal interconversion by means of the replacement of one bridging hydride or sulfide ligand in the respective {Pt(mu-H)(mu-S)Pt} and {Pt(mu-S)2Pt} cores enables the closure of the reaction cycle involving complexes 1-5. Theoretical calculations support the existence of the undetected intermediates proposed for conversion from 1 to 2 and from 3 to 2 and also account for the fluxional behavior of 1 in solution. The intermediates proposed are consistent with the experimental results obtained in comparable reactions carried out with labeled reagents, which have provided evidence that complex 1 is the source of the hydride ligands in complexes 2 and 3. Overall, our results show the strong dependence on the experimental conditions for the formation of complexes 1-5 as well as for their further conversion in solution.

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“…Closely related analogues with alternative phosphine ligands are known to behave in the same way [2][3][4][5]. Through such reactions, larger homo-and hetero-metallic sulfido-bridged aggregates of higher nuclearities can easily be assembled.…”

Section: Introductionmentioning

confidence: 97%

Spanning [Pt2(μ-S)2(PPh3)4] metalloligands with 1,4-dimercurated durene

Cameron

Linklater

Henderson

et al. 2008

Journal of Organometallic Chemistry

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a b s t r a c tReaction of the metalloligand [Pt 2 (l-S) 2 (PPh 3 ) 4 ] with 0.5 mol equivalents of durene-1,4-bis(mercuric acetate) [AcOHgC 6 Me 4 HgOAc] in methanol gives the polynuclear complex [{Pt 2 (l-S) 2 (PPh 3 ) 4 } 2 (l-1,4-C 6 Me 4 Hg 2 )] 2+ , isolated as its PF À 6 and BPh À 4 salts. Positive-ion ESI mass spectra indicate that [{Pt 2 (l-S) 2 (PPh 3 ) 4 } 2 (l-1,4-C 6 Me 4 Hg 2 )] 2+ undergoes fragmentation by successive loss of PPh 3 ligands, while the ESI mass spectrum of the BPh À 4 salt showed additional ions [Pt 2 (l-S) 2 (PPh 3 ) 4 (HgC 6 Me 4 HgPh)] + and [Pt 2 (l-S) 2 (PPh 3 ) 4 HgPh] + as a result of phenyl transfer from BPh À 4 to Hg. A single-crystal X-ray structure determination on [{Pt 2 (l-S) 2 (PPh 3 ) 4 } 2 (l-1,4-C 6 Me 4 Hg 2 )](BPh 4 ) 2 shows that the cation crystallises on a centre of symmetry, with structural features that are comparable to those of the previously characterised complex [Pt 2 (l-S) 2 (PPh 3 ) 4 HgPh]BPh 4 .

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Extending The Reaction Landscape of the {Pt(μ‐S)₂Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

Cited by 47 publications

References 80 publications

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

Reaction Chemistry of Complexes Containing PtH, PtSH, or PtS Fragments: From Their Apparent Simplicity to the Maze of Reactions Underlying Their Interconversion

Spanning [Pt2(μ-S)2(PPh3)4] metalloligands with 1,4-dimercurated durene

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Extending The Reaction Landscape of the {Pt(μ‐S)2Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

Cited by 47 publications

References 80 publications

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

C–S Bond Activation and Partial Hydrogenation of Thiophene by a Dinuclear Trihydride Platinum Complex

Reaction Chemistry of Complexes Containing PtH, PtSH, or PtS Fragments: From Their Apparent Simplicity to the Maze of Reactions Underlying Their Interconversion

Spanning [Pt2(μ-S)2(PPh3)4] metalloligands with 1,4-dimercurated durene

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Extending The Reaction Landscape of the {Pt(μ‐S)₂Pt} Core: From Metal Centers to Non‐Metallic Electrophiles