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• W1997615090 endingPage "522" @default.
• W1997615090 startingPage "507" @default.
• W1997615090 abstract "Abstract The dialkyl compound cis ‐dimethyl[(sulfinyl‐ κS )bis[methane]][tris(2‐methylphenyl)phosphine]platinum(2+) ( cis ‐[Pt(Me) 2 (dmso)(P( o ‐tol) 3 ]; 1 ) has been isolated from the reaction of cis ‐dimethylbis[(sulfinyl‐ κS )bis[methane]]platinum(2+) ( cis ‐[Pt(Me) 2 (dmso) 2 ]) with tris(2‐methylphenyl)phosphane (P( o ‐tol) 3 ). Restricted rotation around the PC ipso bonds of the phosphane ligand generates two different conformers, 1a and 1b , in rapid exchange in non‐polar solvents at low temperature. Strong through‐space contacts between the ortho ‐Me substituent groups on the ligand and the cis ‐Me groups in the coordination plane were determined, which proved useful for identifying the atropisomers formed. At room temperature, 1 H‐NMR spectra of 1 maintain a ‘static’ pattern upon onset of easy and rapid ortho ‐platination, leading to [[2‐[bis(2‐methylphenyl)phosphino‐ κP ]phenyl]methyl‐ κC ]methyl[(sulfinyl‐ κS )bis[methane]]platinum(2+) ( 2 ), a new C,P‐cyclometalated compound of platinum(II), with liberation of methane. The process has been studied by 1 H‐ and 31 P{ 1 H}‐NMR in CDCl 3 , and kinetics experiments were performed by conventional spectrophotometric techniques. The first‐order rate constants k c decrease with the addition of dimethyl sulfoxide until the process is blocked by the presence of a sufficient excess of sulfoxide. This behavior reveals a mechanism initiated by ligand dissociation and formation of a three‐coordinate species. The value of the rate constant for dimethyl sulfoxide dissociation k 1 has been measured independently over a wide temperature range by both 1 H‐NMR ligand exchange (isotopic labeling experiments) and ligand substitution (stopped‐flow pyridine for dimethyl sulfoxide substitution). The rates of the two processes are in reasonable agreement at the same temperature, and a single Eyring plot can be constructed with the two sets of kinetics data. However, the value of the derived dissociation constant at 308 K ( k 1 =6.5±0.3 s −1 ) is at least two orders of magnitude higher than that of cyclometalation ( k c =0.0098±0.0009 s −1 at 308 K). Clearly, the dissociation step is not rate‐determining for cyclometalation. A multistep mechanism consistent with mass‐law retardation is derived, which involves a pre‐equilibrium that controls the concentration of an unsaturated three‐coordinate, 14‐electron T‐shaped cis ‐[PtMe 2 {P( o‐ tol) 3 }] intermediate. Cyclometalation is initiated in this latter by an agostic interaction with the σ (CH) orbital of a methyl group. Oxidative addition of the CH bond follows, yielding a cyclometalated‐hydrido 16‐electron Pt(IV) five‐coordinate intermediate. Finally, reductive elimination and re‐entry of dimethyl sulfoxide with liberation of methane should yield the cyclometalated species 2 ." @default.
• W1997615090 created "2016-06-24" @default.
• W1997615090 creator A5004301405 @default.
• W1997615090 creator A5041210370 @default.
• W1997615090 creator A5078495537 @default.
• W1997615090 date "2005-03-01" @default.
• W1997615090 modified "2023-10-18" @default.
• W1997615090 title "A Dissociative Route to C?H Bond Activation: Ligand Cyclometalation incis-Dimethyl[(sulfinyl-?S)bis[methane]][tris(2-methylphenyl)phosphine]platinum(2+)" @default.
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• W1997615090 doi "https://doi.org/10.1002/hlca.200590035" @default.
• W1997615090 hasPublicationYear "2005" @default.
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