Exclusive Csp3–Csp3 vs Csp2–Csp3 Reductive Elimination from PtIV Governed by Ligand Constraints

Bowes, Eric G.; Pal, Shrinwantu; Love, Jennifer A.

doi:10.1021/jacs.5b10993

Cited by 34 publications

(33 citation statements)

References 26 publications

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“…It can be expected that the selectivity for reductive elimination from square pyramidal d 6 complexes by sp 3 -sp 2 coupling versus sp 3 -sp 3 coupling will depend on how easily the sp 2 group (Ph or C 6 H 4 in the present work) can attain the orientation orthogonal to the sp 3 M-R bond needed to form the C-C bond between these groups. [5][6][7][8][9][10][11][12] In turn, this will depend on steric interactions with the other ligands (bipy in the present work), and it should be possible to design ligands to switch the selectivity between sp 3 -sp 2 and sp 3 -sp 3 coupling, with potentially useful applications in catalysis. 7.…”

Section: All Of the Cationic Five-coordinate Intermediates [Mrr=r==(bmentioning

confidence: 99%

“…Thus, complexes of general formula [MXRR= 2 L 2 ] or [MXRR=R==L 2 ] (L = neutral ligand, X = anionic ligand, R,R= = alkyl or aryl) can often be prepared by oxidative addition of an alkyl halide RX to [MR= 2 L 2 ] or [MR=R==L 2 ], respectively. [5][6][7][8][9][10][11][12] In many cases, subsequent reductive elimination reactions occur in accordance with the simple rules of Ananikov et al, described above. 4a An example from the recent literature is shown in Scheme 1a, in which Me-aryl (sp 3 -sp 2 ) coupling is favored over Me-CH 2 (sp 3 -sp 3 ) coupling.…”

Section: Introductionmentioning

confidence: 99%

“…4a An example from the recent literature is shown in Scheme 1a, in which Me-aryl (sp 3 -sp 2 ) coupling is favored over Me-CH 2 (sp 3 -sp 3 ) coupling. 7 However, there are also many exceptions 6,9,11 and two examples in which Me-Me (sp 3 -sp 3 ) coupling is favored over Me-aryl (sp 3 -sp 2 ) coupling are shown in Schemes 1b and 1c. 6a,9 In other cases, there may be a competition between the two possible reactions.…”

Section: Introductionmentioning

confidence: 99%

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Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Puddephatt

2019

Can. J. Chem.

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The isomerization and reductive elimination reactions from octahedral organometallic complexes of palladium(IV) and platinum(IV) usually occur through five-coordinate intermediates that cannot be directly detected. This paper reports a computational study of five-coordinate complexes of formulae [PtMe3(bipy)]+, [PtMe2Ph(bipy)]+, and [PtMe(CH2CMe2C6H4)(bipy)]+ (M = Pd or Pt, bipy = 2,2′-bipyridine), particularly with respect to reactivity and selectivity in reductive elimination. All of the complexes are predicted to have square pyramidal structures with the bipy and two R groups in the equatorial positions and one R group in the axial position, and axial–equatorial exchange occurs by a pairwise mechanism, with the transition state having a pinched trigonal bipyramidal (PTBP) stereochemistry, with one nitrogen and two R groups in the trigonal plane. The activation energy for isomerization is lower than that for reductive elimination in all cases. For the complexes [MMe2Ph(bipy)]+, the activation energies for reductive elimination with Me–Me or Me–Ph coupling are similar. For the complexes [MMe(CH2CMe2C6H4)(bipy)]+, the reductive elimination with Me–C6H4 bond formation from the isomer with the methyl group in the axial position is predicted and is attributed to it having the best conformation of the Me and C6H4 groups for C–C bond formation. In all cases, the selectivity for reductive elimination is similar for M = Pd or Pt, but reactivity is higher for M = Pd. The relevance of this work to selectivity in catalysis is discussed.

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Section: All Of the Cationic Five-coordinate Intermediates [Mrr=r==(bmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Puddephatt

2019

Can. J. Chem.

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“…The synthetic route illustrated in Scheme 3 is a convenient alternative to the use of expensive methyl- d 3 lithium or magnesium reagents for the synthesis of [(CD 3 ) 2 Pt II (μ-SMe 2 )] 2 . 44 …”

Section: Resultsmentioning

confidence: 99%

Reversible Pt^II–CH₃ deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted Pt^II-protonation

et al. 2021

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“…The elimination reduction processes in hexa-coordinate Pt(IV) complexes, as well as in Pd(IV) ones, are known to pass through the loss of a ligand to generate a fivecoordinate intermediate as preliminary step [18][19][20][21][22][23][24] and five-coordinate Pt(IV) complexes are now well recognized species. [25][26][27][28][29][30][31][32] The synthesis of complexes 2-5 can be envisaged to start with the coordination of a good nucleophile, the L^Sanion, to one of the Pt (III) centres affording a formally Pt(II),Pt(IV) unsaturated complex in which the L^Sligand is terminally bonded to Pt(IV).…”

Section: Reaction Of [(R F )mentioning

confidence: 99%

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

et al. 2017

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The outcome of the reaction of the Pt(III),Pt(III) complex [(C 6 F 5) 2 Pt III (µ-PPh 2) 2 Pt III (C 6 F 5) 2 ](Pt-Pt) (1) with the S-based anions thiophenoxide (PhS-), ethyl xanthogenate (EtOCS 2-), 2-mercaptopyrimidinate (pymS-) and 2-mercaptopyridinate (pyS-) was found dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [N n Bu 4 ][(R F) 2 Pt II (μ-PhS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (2), [N n Bu 4 ][(R F) 2 Pt II (μ-EtOCS 2-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (3), [N n Bu 4 ][(R F) 2 Pt II (μ-pymS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (4) or [N n Bu 4 ][(R F) 2 Pt II (μ-pyS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (5), respectively (R F = C 6 F 5). Complexes 2-5 display new Ph 2 P(SL) ligands exhibiting a κ 2-P,S bridging coordination mode, which derive from a reductive elimination of a PPh 2 group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS 2 and pymSmonobridged complexes [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (EtOCS 2)(R F)] (6) and [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (pymS)(R F)] (7), respectively, which derive from a reductive elimination of a PPh 2 group with a pentafluorophenyl ring. The reaction of 1 with EtOCS 2 K in acetonitrile yielded a mixture of 3 and 6 as a consequence of the concurrence of two processes: a) the formation of 3 by a reaction that parallels the formation of 3 by 1 plus EtOCS 2 K in acetone; b) the transformation of 1 into the neutral complex [(PPh 2 R F)(CH 3 CN)(R F)Pt II (μ-PPh 2)Pt II (R F) 2 (CH 3 CN)] (8), which, on turn, reacts with EtOCS 2 K to give 6. The 1 to 8 transformation was found to be fully reversible. In fact, dissolving 8 in acetone or dichloromethane afforded pure 1 after solvent evaporation or 2 crystallisation with n-hexane. The XRD structures of 2, 3, 4, 6, 7 and 8 were determined and the behaviour in solution of the new complexes is discussed.

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Exclusive Csp³–Csp³ vs Csp²–Csp³ Reductive Elimination from Pt^IV Governed by Ligand Constraints

Cited by 34 publications

References 26 publications

Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Reversible Pt^II–CH₃ deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted Pt^II-protonation

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

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Exclusive Csp3–Csp3 vs Csp2–Csp3 Reductive Elimination from PtIV Governed by Ligand Constraints

Cited by 34 publications

References 26 publications

Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

Reversible PtII–CH3 deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted PtII-protonation

Solvent-Driven P–S vs P–C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions

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Exclusive Csp³–Csp³ vs Csp²–Csp³ Reductive Elimination from Pt^IV Governed by Ligand Constraints

Reversible Pt^II–CH₃ deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted Pt^II-protonation