Characterization of PtH3(PtBu3)2+ as the First Dihydrogen Complex of d8, Pt(II)

Gusev, Dmitry G.; Notheis, J. U.; Rambo, Joe R.; Hauger, Bryan E.; Eisenstein, Odile; Caulton, Kenneth G.

doi:10.1021/ja00095a055

Cited by 43 publications

(46 citation statements)

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“…The 1 H NMR spectrum of 6 exhibits one signal at δ =2.74 ppm with J (H,Pt)=15.0 Hz for the o ‐methyl groups and one triplet at δ =−19.74 ppm ( 2 J (H,P)=10.0 Hz) with a 1 J (H,Pt) coupling constant of 2074 Hz. The data is similar to that of the three‐coordinate derivatives [PtH(P t Bu 3 ) 2 ]X (X=BF 4 , PF 6 , ClO 4 , CF 3 SO 3 )5 but differs from that of the related cyclohexyl species [PtH(PCy 3 ) 2 (L)][BAr f 4 ] (L=CD 2 Cl 2 and H 2 )6a indicating that 5 and 6 are not solvato or dihydrogen19 complexes of platinum( II ), but are actually three‐coordinate complexes with time‐averaged agostic interactions of the four o‐ methyl groups. When the solutions containing either 5 or 6 are gently heated (40 °C) under Ar for a few minutes, the equilibrium completely shifts to the left as a result of the deprotonation of an agostic o ‐methyl group and associated H 2 extrusion.…”

Section: Methodssupporting

confidence: 55%

“…In the reversible PtC hydrogenolysis, H 2 probably replaces the agostic o‐ methyl group, which leads to a transient cationic dihydrogen‐cyclometalated platinum( II ) complex that may be in equilibrium with the 16‐electron platinum( IV ) dihydrido species 1j. 19 Interestingly, Milstein and co‐workers have recently reported the opening of a platinum( II ) metallacycle complex by reaction with dihydrogen, but under harsher conditions 20…”

Section: Methodsmentioning

confidence: 99%

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Novel T‐Shaped 14‐Electron Platinum(II) Complexes Stabilized by One Agostic Interaction

et al. 2003

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The stereoelectronic properties of the PR2(2,6‐Me2C6H3) (R=Ph, Cy) ligand can be used to stabilize an unprecedented class of 14‐electron platinum(II) complexes. The X‐ray analysis of the cyclometalated cyclohexyl derivative reveals an agostic interaction between the Pt center and an o‐methyl moiety (see picture). The fast and reversible formation of three‐coordinate platinum–hydrido complexes occurs by reaction with H2, and is achieved through the cleavage of a platinum–carbon bond.

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Section: Methodssupporting

confidence: 55%

Section: Methodsmentioning

confidence: 99%

Novel T‐Shaped 14‐Electron Platinum(II) Complexes Stabilized by One Agostic Interaction

et al. 2003

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“…In contrast, computations on PtH 3 L 2 + (L = phosphine) showed a clear preference for a square planar Pt(II)(H)(H 2 )L 2 + structure. [49] The calculations were carried out by Joe Rambo, a post-doctoral fellow from Indiana University. His MP2/DFT optimized structure gave a dihydrogen-hydride complex.…”

Section: Hydride and Di-hydrogen Interactionmentioning

confidence: 99%

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

Eisenstein

2022

Israel Journal of Chemistry

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This rosarium article relates the adventure started 50 years ago of a computational chemist who was interested in molecules; what are they, what are their shape and how do they react. The story describes results, still valid today, obtained with highly simplified models of chemical reality and elementary computational methods and the gain resulting from the use of better models and more elaborate computational methods. It was necessary to select examples. In this presentation, focus is on hydride and dihydrogen complexes as well as on nucleophiles. Nucleophiles were considered as free hydrides in gas phase at the start of the rosarium while the Grignard reaction is treated with ab initio molecular mechanisms at the end of it.

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“…17 Caulton and co-workers reported the first d 8 dihydrogen complex, a cationic platinum(II) complex, in 1994. 18 Heinekey and co-workers characterized a Co(H 2 ) complex in 2011, 19 and the first Pd(H 2 ) complex was reported in 2015. 20 Evidence for dihydrogen complexes of nickel was lacking until characterization of a Ni(H 2 ) complex by Caulton and co-workers in 2010.…”

Section: ■ Introductionmentioning

confidence: 99%

Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

et al. 2015

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Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.

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Characterization of PtH3(PtBu3)2+ as the First Dihydrogen Complex of d8, Pt(II)

Cited by 43 publications

References 0 publications

Novel T‐Shaped 14‐Electron Platinum(II) Complexes Stabilized by One Agostic Interaction

Novel T‐Shaped 14‐Electron Platinum(II) Complexes Stabilized by One Agostic Interaction

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

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