Quantitative recovery of dihydrogen from hydrogen sulphide using the complexes, [Pd2X2(µ-dppm)2][X = Cl, Br, l; dppm = bis(diphenylphosphino)methane]

Lee, Chung-Li; Besenyei, Gábor; James, Brian R.; Nelson, David A.; Lilga, Michael A.

doi:10.1039/c39850001175

Cited by 19 publications

(10 citation statements)

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“…The occupancy factors for oxygen atom disorder were refined to 0.66 for O(1) and 0.34 for O(2), a feature also observed for 5 and 8. The S-O bond distance is 142.8 pm, comparable to those found for 5 (140 pm) 17,18 and 8 (144, 146 pm). Complex 3a contains pyramidal S, located equidistant from both metal centers.…”

supporting

confidence: 80%

“…The occupancy factors for oxygen atom disorder were refined to 0.66 for O(1) and 0.34 for O(2), a feature also observed for 5 and 8. The S-O bond distance is 142.8 pm, comparable to those found for 5 (140 pm) 17 13) and C(38) on the same side of the P-Pt-P-P-Pt-P plane. Two Pt and four P atoms are planar within 9 pm.…”

supporting

confidence: 75%

“…This reaction was successful, providing what we believe is the first μ-SO complex of platinum. Related complexes have been made with Pd , and Ni, not through direct SO insertion but by oxidation of a μ-S complex. With that in mind, we carried out a parallel (and superior) synthesis of 3 based on an oxidation reaction, eq 3.…”

mentioning

confidence: 99%

“…The Pt−S distances, 226.2 pm, are equal. Structures of these binuclear A-frame bis(diphenylphosphino)methane (dppm) complexes have been reported: Pd 2 Cl 2 (μ-SO)(μ-dppm) 2 ( 5 ), , Pd 2 Cl 2 (μ-SO 2 )(μ-dppm) 2 ( 6 ), Pd 2 Cl 2 (μ-S)(μ-dppm) 2 ( 7 ), Ni 2 Cl 2 (μ-SO)(μ-dppm) 2 ( 8 ), Ir 2 (CO) 2 (μ-N-tol)(μ-dppm) 2 , and Rh 2 (CO) 2 (μ-S)(μ-dppm) 2 …”

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confidence: 99%

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Two Routes to Bis(μ-diphenylphosphino)methane Diplatinum Halides Bridged by Sulfur Monoxide

1999

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The use of simple chemical methods to generate and study reactive molecules has attracted some attention, but relatively little attention has been paid to sulfur monoxide. 1,2 Until now, the main method for generating SO has been the pyrolysis of episulfoxides 1,3-5 and other sulfoxides of varying structures. 6,7 The reactive SO molecule has been trapped as a thiophene-1-oxide with dienes and trienes. 8,9 Certain transition metal complexes have also been used to trap SO. 10 Atoms and small molecules are known to insert into the Pt-Pt bond of the platinum(I) complex Pt 2 (µ-dppm) 2 X 2 , 1 (X ) Cl, Br, I), to produce so-called A-frame molecules Pt 2 (µ-dppm) 2 X 2 (µ-Y), 2, Y ) S, SO 2 , CH 2 (from CH 2 N 2 ), CO, We recently uncovered a reaction (eq 1) that gradually generates SO in solution. 16 Sulfur monoxide was then either oxidized or, in separate experiments, trapped with a diene. We reasoned that SO logically could also be trapped by the Pt(I) complex 1, eq 2, to form Pt 2 (µ-dppm) 2 (µ-SO), 3.This reaction was successful, providing what we believe is the first µ-SO complex of platinum. Related complexes have been made with Pd 17,18 and Ni, 19 not through direct SO insertion but by oxidation of a µ-S complex. With that in mind, we carried out a parallel (and superior) synthesis of 3 based on an oxidation reaction, eq 3.The lemon-yellow compounds 1 and the yellow 2 (µ-S) were prepared by established procedures. 20,21 From reaction 3 22 a pure yellow product, 3a, was isolated in 92% yield. Recrystallization from chloroform-hexane afforded yellow crystals. The product was identified and characterized by elemental analysis, NMR, 23 and singlecrystal X-ray diffraction. 24 The iodide derivative 3b was similarly obtained in 86% yield as a yellow solid and (1) Abu-Yousef, I. A.; Harpp, D. N. Brown, M. P.; Puddephatt, R. J.; Rashidi, M.; Seddon, K. R. J. Chem. Soc., Dalton Trans. 1977, 951. (21) Brown, M. P.; Fisher, J. R.; Franklin, S. J.; Puddephatt, R. J. J. Chem. Soc., Chem. Commun. 1978, 749. (22) Compound 2a (250 mg, 0.20 mmol) and MTO (2.5 mg, 10 µmol) in 15 mL of chloroform were treated with 1 equiv of hydrogen peroxide.

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supporting

confidence: 80%

“…The occupancy factors for oxygen atom disorder were refined to 0.66 for O(1) and 0.34 for O(2), a feature also observed for 5 and 8. The S-O bond distance is 142.8 pm, comparable to those found for 5 (140 pm) 17 13) and C(38) on the same side of the P-Pt-P-P-Pt-P plane. Two Pt and four P atoms are planar within 9 pm.…”

supporting

confidence: 75%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Two Routes to Bis(μ-diphenylphosphino)methane Diplatinum Halides Bridged by Sulfur Monoxide

1999

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“…The interactions of organosulfur compounds with transition metal complexes are important in the biological sulfur cycle, and in hydrodesulfurisation catalysis, and are relevant in the potential for H 2 recovery from H 2 S. 1 In 1985, we reported the solution reaction of Pd 2 Cl 2 (m-dppm) 2 with H 2 S that quantitatively gives the "A-frame" bridged-sulfide complex, Pd 2 Cl 2 (m-S)(m-dppm) 2 and H 2 . 2 As a continuation of our investigations into these types of reactions, [1][2][3] we now report the prototype of a new class of Pd I 2 compounds based on the potentially P 2 N 4hexadentate, but in this instance functionally tetradentate ligand, dmapm, 4 i.e., Pd 2 Cl 2 (m-N,P,P,N-dmapm) (1). Further, reaction of 1 with thiols provides the first example of oxidative addition of RS-H across a phosphine-bridged Pd I -Pd I bond.…”

mentioning

confidence: 95%