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Volumn 14, Issue 35, 2008, Pages 11050-11060

"Roll-over" cyclometalation of 2,2′-bipyridine platinum(II) complexes in the gas phase: A combined experimental and computational study

Author keywords

Bipyridtne; Bond activation; Cyclometalation; Dehydrosulfurization; Platinum

Indexed keywords

ATOMIC PHYSICS; ATOMS; CHEMICAL BONDS; DYES; EXPERIMENTS; HYDROCARBONS; HYDROGEN; HYDROGEN BONDS; LIGANDS; PLATINUM; SULFUR;

EID: 57149137510     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200801658     Document Type: Article
Times cited : (55)

References (88)
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    • While the present experiments do not allow to assign a specific structure to [1-CH4-C2H4, DFT calculations predict the PtIl compound, bipy)Pt(SH2, as the most stable isomer compared to [Pt(bipy-H)(SH2, 64 kJmol-1 higher in energy) and the formal Pt(IV) species [Pt(bipy)(S)H, 111 kJmol-1 higher in energy
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    • For further details of the appearance energy measurements, see: reference [14
    • For further details of the appearance energy measurements, see: reference [14].
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    • We note, that dehydrosulfurization (DHS) is formally related to the industrially extremely important hydrodesulfurization (HDS) reaction of organic sulfur compounds: a) D. Stirling, The Sulfur Problem: Cleaning up Industrial Feedstocks, RSC Clean Technology Monographs, Royal Society of Chemistry, Cambridge, 2000;
    • We note, that dehydrosulfurization (DHS) is formally related to the industrially extremely important hydrodesulfurization (HDS) reaction of organic sulfur compounds: a) D. Stirling, The Sulfur Problem: Cleaning up Industrial Feedstocks, RSC Clean Technology Monographs, Royal Society of Chemistry, Cambridge, 2000;
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    • For recent, systematic experimental/computational studies of mechanistic variants of gas-phase, metal-mediated C-H bond activation, see:
    • For recent, systematic experimental/computational studies of mechanistic variants of gas-phase, metal-mediated C-H bond activation, see:
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    • Although [Pt(bipy)(S)(H, is not the most stable isomer, 22] the calculated reaction pathway can explain the experimental result of ethene liberation in the reaction of 2 with dimethylsulfide. An isomerisation process [Pt(bipy)(S)(H, →[Pt(bipy)SH, was therefore not further investigated
    • + was therefore not further investigated.
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    • Also interesting in this context are the following references about the dissociation and thermolysis of dimethylsulfide: a L. G. S. Shum, S. W. Benson. Int. J. Chem. Kinet. 1985, 17, 749-761;
    • Also interesting in this context are the following references about the dissociation and thermolysis of dimethylsulfide: a) L. G. S. Shum, S. W. Benson. Int. J. Chem. Kinet. 1985, 17, 749-761;


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