1993
DOI: 10.1021/om00031a037
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Kinetics and conformation in the reversible insertion of an alkene into a platinum-carbon bond in a chelated (pentenyl)platinum complex

Abstract: The synthesis and characterization, including detailed 'H, 2H, 31P, and 13C NMR analysis of [ (l,l-dideuteri0-2,2-dimethyl-4-penten-l-yl-K3C~~~*~) (dmpe)PtnlBF4, 1-adz, and its 3,3-dideuterio isotopomer, 1 -7 4 (dmpe = 1,2-bis(dimethylphosphino)ethane), are described. Thermolysis of each 1-a-dz and 1-y-dz was carried out a t 125 "C in several solvents to yield a 1/1 mixture of 1-a-dz and 1-ydz. The rate of rearrangement is cleanly first order. Thermolysis of 1-a-d2 between 81 and 125 "C in methylene chloride l… Show more

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Cited by 36 publications
(39 citation statements)
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“…[16] Thus, rhodium compound 2 might resemble a structure on the pathway of b-carbon elimination at d 8 -ML 2 templates. [17] Owing to the averaging out of all nine methyl protons of the Np group by tBu and Me rotations, lowered C ± H streching frequencies, upfield NMR shifts, or reduced 13 C ± 1 H coupling constants for the agostic hydrogen atoms are not observed for 2. [15] However, agostic interactions are unequivocally established for the solid-state structure and by all NMR data of 2 in solution.…”
Section: Methodsmentioning
confidence: 99%
“…[16] Thus, rhodium compound 2 might resemble a structure on the pathway of b-carbon elimination at d 8 -ML 2 templates. [17] Owing to the averaging out of all nine methyl protons of the Np group by tBu and Me rotations, lowered C ± H streching frequencies, upfield NMR shifts, or reduced 13 C ± 1 H coupling constants for the agostic hydrogen atoms are not observed for 2. [15] However, agostic interactions are unequivocally established for the solid-state structure and by all NMR data of 2 in solution.…”
Section: Methodsmentioning
confidence: 99%
“…3).While many cycloalkylmethyl complexes of transition metals undergo easy ring opening, complexes 2 and 3 were not decomposed over one hour in refluxing methanol solution. The ring-opening may require a vacant coordination site at platinum [7,18,32], so the complexes were treated first with silver trifluoroacetate to give the complexes [PtMe 2 (CH 2 R)(O 2 CCF 3 )(bipy)], 7, R=c-C 3 H 5 ; 8, R=c-C 4 H 7 ; 9, R=CH 2 CH 2 CH=CH 2 ; 10, R=CH 2-CH=CHMe, which contain the more weakly bound trifluoroacetate ligand. These complexes were all thermally stable in solution at room Inorganic Chemistry Communications j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e temperature, and the cyclobutyl derivative 8 was also stable in refluxing methanol but the cyclopropyl derivative 7 did undergo ringopening to give 9 (as a mixture of isomers 9a and 9b, Scheme 2) under these conditions.…”
mentioning
confidence: 99%
“…4. The cyclopropyl ring strain provides the driving force for the ring opening reaction (it can be considered as a β-carbon elimination [16][17][18]) to convert 2 to the 3-butenyl isomer 4a, but there is no easy pathway for the 18-electron complex to react. The E-2-butenyl complex 5 is expected to be slightly more stable than 4a and is the most stable of the isomeric complexes with linear C 4 H 7 groups.…”
mentioning
confidence: 99%
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