Synthesis and characterization of dinuclear trihydride complexes of platinum with chelating ligands. Crystal and molecular structure of [Pt2H3(Ph2P(CH2)2PPh2)2][BPh4]

Knobler, Carolyn B.; Kaesz, H. D.; Minghetti, Giovanni; Bandini, Anna Laura; Banditelli, Guido; Bonati, Flavio

doi:10.1021/ic00158a021

Cited by 50 publications

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“…[16b, 15,20] Commercial Na 2 S, Na 2 S·9 H 2 O, NaBH 4 , and NaBD 4 compounds were used without further purification. NaSH was obtained from commercial NaSH·x H 2 O by keeping it under vacuum overnight.…”

Section: Methodsmentioning

confidence: 99%

“…Complex 1 was synthesized in high yields by using a onepot reaction procedure that involves the mixing of [PtCl 2 - The synthetic procedure we followed to obtain 1 has already been reported for the [Pt 2 (H) 3 A C H T U N G T R E N N U N G (dcype) 2 ]X (dcype = 1,2-bis(dicyclohexylphosphanyl)-ethane; X = BF 4 , Cl, OH, and BPh 4 ) analogues, [14] and affords much better yields than the two synthetic alternatives used to obtain [Pt 2 (H) 3 A C H T U N G T R E N N U N G (dppp) 2 ]BF 4 , [15] which includes the same diphosphane ligand as 1. Addition of the sodium salts of BF 4 À , BPh 4 À , or PF 6 À instead of ClO 4 À led us to unsatisfactory yields, and that of Cl À reversed the reaction by causing formation of the starting complex [PtCl 2 A C H T U N G T R E N N U N G (dppp)].…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

“…However, the same cationic complex as that found in 1 had already been reported as the tetrafluoroborate salt. [15] Spectroscopic data for compounds 1, [15] 3, [16b] 4, [20] [20] and [Pt(SH) 2 …”

Section: H T U N G T R E N N U N G (M-h)a C H T U N G T R E N N U N Gmentioning

confidence: 99%

“…[15] Both, the crystal structure of 1 and the theoretical calculations that account for this dynamic process are discussed below. …”

Section: A C H T U N G T R E N N U N G (Dppp)]mentioning

confidence: 99%

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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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Section: Methodsmentioning

confidence: 99%

Section: Wwwchemeurjorgmentioning

confidence: 99%

Section: H T U N G T R E N N U N G (M-h)a C H T U N G T R E N N U N Gmentioning

confidence: 99%

“…[15] Both, the crystal structure of 1 and the theoretical calculations that account for this dynamic process are discussed below. …”

Section: A C H T U N G T R E N N U N G (Dppp)]mentioning

confidence: 99%

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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 chemical shift falls in a narrow range (Ϫ1.66 to ϩ0.83 ppm) depending on the diphosphino ligand as in the parent trihydrido complexes, [Pt 2 (P-P) 2 H 3 )] ϩ . 10 The low H-Pt coupling, from 450 to 484 Hz, is consistent with a hydride bridging two PtP 2 moieties.…”

mentioning

confidence: 90%

Multinuclear (¹H,³¹P and¹⁹⁵Pt) NMR study and dynamical analysis of binuclear µ-hydrido µ-carbonyl Pt(i) cations with chelating diphosphines

et al. 2004

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The dynamic behaviour of the binuclear µ-hydrido µ-carbonyl cations with chelating diphosphines, [Pt 2 (P-P) 2 -(µ-H)(µ-CO)]ϩ [P-P = dppe, 1, dppp, 2, and dppb H results are consistent with intramolecular mutual exchange of the P atoms with respect to the bridging ligands in all of the complexes 1-3. A detailed dynamical analysis carried out on complexes 2 and 3 shows that the dynamical process exchanges the P atoms within a single diphosphino ligand, and excludes the simultaneous P atom exchange in both ligands. The bite of the diphosphino ligands affects the rate of this process in the order 3 > 2 > 1. The process follows an activation law with ∆H ‡ = 67 and 60 kJ mol Ϫ1 for 2 and 3, respectively, so that P-Pt bond breaking should not be involved. The positive activation entropy (17-19 J K Ϫ1 mol Ϫ1 ) hints at a mechanism where the intermediate(s) have a less ordered structure than that of the stable complex. In accordance with the NMR results, two reactivity experiments provided further evidence of the intramolecular nature of the observed dynamics and exclude any equilibration path via Pt-P and/or Pt-Pt bond breaking. On these grounds, a mechanism involving rotation about a Pt-Pt bond could be proposed.

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μ‐Hydrido‐tetrakis(tertiary phosphine)diplatinum Cations

Chaloupka

Venanzi

Cowan

et al. 1990

Inorganic Syntheses

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Synthesis and characterization of dinuclear trihydride complexes of platinum with chelating ligands. Crystal and molecular structure of [Pt2H3(Ph2P(CH2)2PPh2)2][BPh4]

Abstract: Die Darstellung der kationischen Trihydridodiplatimll)‐Komplexe (IIa) erfolgt durch Behandlung des dikationischen Bis‐[pyrazoll‐PtUU‐Monomeren (I) mit KBH4.

Cited by 50 publications

References 0 publications

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

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

Multinuclear (¹H,³¹P and¹⁹⁵Pt) NMR study and dynamical analysis of binuclear µ-hydrido µ-carbonyl Pt(i) cations with chelating diphosphines

μ‐Hydrido‐tetrakis(tertiary phosphine)diplatinum Cations

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Synthesis and characterization of dinuclear trihydride complexes of platinum with chelating ligands. Crystal and molecular structure of [Pt2H3(Ph2P(CH2)2PPh2)2][BPh4]

Abstract: Die Darstellung der kationischen Trihydridodiplatimll)‐Komplexe (IIa) erfolgt durch Behandlung des dikationischen Bis‐[pyrazoll‐PtUU‐Monomeren (I) mit KBH4.

Cited by 50 publications

References 0 publications

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

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

Multinuclear (1H,31P and195Pt) NMR study and dynamical analysis of binuclear µ-hydrido µ-carbonyl Pt(i) cations with chelating diphosphines

μ‐Hydrido‐tetrakis(tertiary phosphine)diplatinum Cations

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Multinuclear (¹H,³¹P and¹⁹⁵Pt) NMR study and dynamical analysis of binuclear µ-hydrido µ-carbonyl Pt(i) cations with chelating diphosphines