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• W2050489332 abstract "Abstract The neutral complexes of formula [κ 2 P , S ‐(dppmS)Pt(CH 3 )(Cl)] ( 1 ), [κ 2 P , S ‐(dppeS)Pt(CH 3 )(Cl)] ( 2 ) and [κ 2 P , S ‐(dpppS)Pt(CH 3 )(Cl)] ( 3 ) [dppmS = Ph 2 PCH 2 P(S)Ph 2 ; dppeS = Ph 2 P(CH 2 ) 2 P(S)Ph 2 ; dpppS = Ph 2 P(CH 2 ) 3 P(S)Ph 2 ] are active catalyst precursors for the hydroformylation of 1‐octene in methyl isobutyl ketone. The order of reactivity found is 3 > 2 > 1 . Surprisingly, the cationic complexes [κ 2 P , S ‐(dppeS)Pt(CH 3 )(CH 3 CN)]BF 4 ( 4a ) and [{κ P ,μ‐κ S ‐(dppeS)Pt(CH 3 )} 2 ][BF 4 ] 2 ( 5 ) are less active than the analogous neutral complex 2 . High‐pressure NMR studies revealed that, at 20 °C under 1 to 50 bar of syngas, and in the presence of SnCl 2 , both 2 and 4a react immediately to form the same acetyl complex ( 8 ). However, in the absence of SnCl 2 , the methyl carbonyl complex [κ 2 P , S ‐(dppeS)Pt(CH 3 )(CO)] + ( 9 ), which is formed from 4a and CO, does not undergo insertion to give the acetyl complex, even under 50 bar of syngas. Thus, the role of SnCl 2 is not only to create a vacant site for CO coordination and to lower the energy barrier for the hydrogenolysis, but also to assist migration of the alkyl group in the CO insertion step. High‐pressure NMR studies of the working reaction solution, under steady‐state conditions, found no evidence for intermediates in which the phosphane sulfide group shows hemilabile behaviour during catalysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)" @default.
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• W2050489332 date "2006-05-17" @default.
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• W2050489332 title "(Diphosphane monosulfide)platinum(<scp>II</scp>) Complexes for Hydroformylation Reactions: Their Catalytic Activity and a High‐Pressure NMR Mechanistic Study" @default.
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• W2050489332 doi "https://doi.org/10.1002/ejic.200501016" @default.
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