Regioselective insertion of acrylonitrile into the platinum-nitrogen bond of hydrido(phenylamido)bis(triethylphosphine)platinum(II). A model step for olefin amination
“…been observed in stoichiometric reactions [146][147][148][149][150][151] or indirectly via deuteriumlabeling experiments [152]. The coupling of these observations with the more prevalent examples of C-H bond formation via reductive elimination over Cheteroatom bond formation by reductive elimination suggests that insertion into the M-amido bond may be preferred.…”
Section: Insertion Route For C-n Bond Formationmentioning
“…been observed in stoichiometric reactions [146][147][148][149][150][151] or indirectly via deuteriumlabeling experiments [152]. The coupling of these observations with the more prevalent examples of C-H bond formation via reductive elimination over Cheteroatom bond formation by reductive elimination suggests that insertion into the M-amido bond may be preferred.…”
Section: Insertion Route For C-n Bond Formationmentioning
“…[100] The PEt 3 -ligated platinum complex [(PEt 3 ) 2 Pt(H)(NHPh)] was shown to react with acrylonitrile at 20 8C in C 6 D 6 to generate an alkyl complex by 2,1-insertion of the acrylonitrile (Scheme 21). Upon warming to 70 8C, this complex underwent CÀH bond-forming reductive elimination to generate the product from one cycle of hydroamination.…”
Section: Reactions Of Metal Amido Complexes With Alkenes For Which DImentioning
Metal-catalyzed addition of an O−H bond to an alkene is a desirable process because it allows for rapid access to ethers from abundant starting materials without the formation of waste, without rearrangements, and with the possibility to control the stereoselectivity. We report the intermolecular, metal-catalyzed addition of phenols to unactivated α-olefins. Mechanistic studies of this rare catalytic reaction revealed a dynamic mixture of resting states that undergo O−H bond oxidative addition and subsequent olefin insertion to form ether products.
“…[3] Furthermore, it is known that nitriles insert into the MoÀCl bond of MoCl 5 , [4] into the ZrÀO bond of [Cp* 2 ZrO], [5] and into EÀN bonds (E B, [6] Al, [7] P, [8] Pt [9] ). Recently, Neumüller et al reported on CsX-catalyzed trimerization reactions of acetonitrile with EMe 3 (E element of Group 13) under elimination of CH 4 and formation of [Me 2 E{HNC(Me)} 2 -steric encumbrance at this site and the fact that an S N 2-type attack on the cyclopropyl carbon C(3) has to pass through a highly strained transition structure.…”
Section: Dedicated To Professor Dieter Sellmann In Occasion Of His 60mentioning
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