Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides

Tate, Brandon K.; Nguyen, Jenna Thu; Bacsa, John; Sadighi, Joseph P.

doi:10.1002/chem.201500870

Cited by 16 publications

(15 citation statements)

References 115 publications

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“…Thus, the reaction follows a second‐order rate law overall such that −d[ 2‐OH ]/d t = k [ 2‐OH ][H 2 ]. This rate expression is similar to that observed for hydrogenolysis of the mononuclear ( t Bu PCP)Pd−OH and dinuclear Ag 2 (μ‐pentoxide) complexes …”

Section: Resultssupporting

confidence: 83%

Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues

Bailey

Phearman

Luconi

et al. 2019

Chemistry A European J

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The hydrogenolysis of mono-and dinuclear Pd II hydroxidesw as investigated both experimentally and computationally.I tw as found that the dinuclear m-hydroxidereact with H 2 to form the analogous dinuclear hydride species {[(PCN R )Pd] 2 (m-H)}(OTf). The dinuclear m-hydride complexes were fully characterized, and are rare examples of structurally characterizedu nsupported singly bridged m-H Pd II dimers. The {[(PCN Me )Pd] 2 (m-OH)}(OTf) hydrogenolysis mechanism was investigated through experimentsa nd com-putations. The hydrogenolysis of the mononuclear complex (PCN H )Pd-OHr esulted in am ixed ligand dinuclears pecies [(PCN H )Pd](m-H)[(PCC)Pd] (PCC = ad ianionic version of PCN H boundt hrough phosphorus P, aryl C, and pyrazole Ca toms) generated from initial ligand "rollover" CÀHa ctivation. Further exposure to H 2 yields the bisphosphine Pd 0 complex Pd[(H)PCN H ] 2 .When the ligand was protected at the pyrazole 5-position in the (PCN Me )PdÀOH complex, no hydride formed under the same conditions;t he reactionp roceeded directly to the bisphosphine Pd 0 complex Pd[(H)PCN Me ] 2 .R eaction mechanisms for the hydrogenolysis of the monomeric and dimerichydroxides are proposed.[a] Dr.Supporting information (selected crystallographic parameters of the solved XRD structures, NMR spectra of all the described compounds, further computationald etails)a nd the ORCID identification number(s) for the author(s) of this article can be found under:h ttps://doi.

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Section: Resultssupporting

confidence: 83%

Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues

Bailey

Phearman

Luconi

et al. 2019

Chemistry A European J

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“…Expanded-ring NHCs, derived from six- and seven-membered cyclic amidinium salts, have been shown to increase the stability of other reactive metal species. − Recently, Whittlesey et al reported that (6Mes)copper(I) hydride (6Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) proved too unstable to isolate but could be trapped efficiently with alkynes or ketones . We now report the synthesis of [(6Dipp)CuH] 2 ( 3a ) and [(7Dipp)CuH] 2 ( 3b ) (6Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; 7Dipp =1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene).…”

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confidence: 78%

Synthesis and Reactivity of New Copper(I) Hydride Dimers

et al. 2016

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The expanded-ring N-heterocyclic carbenes 6Dipp and 7Dipp (6Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene and 7Dipp = 1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene) support isolable neutral copper hydride dimers. [(6Dipp)CuH]2 reacts with 1-hexene to give (6Dipp)copper(I) hexyl by 1,2-insertion and with benzyl isonitrile to afford an η1-formimidoyl by 1,1-insertion.

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“…If electronic effects of the NHC ligands were the dominant factor controlling the insertion rates with CF3CO2Et, then [6CuH]2 would be expected to insert more quickly since saturated expanded-ring NHCs are more electron-donating than unsaturated imidazolylidene NHCs. [28] The stark contrast in insertion rates between [*5CuH]2 and [6CuH]2 or [7CuH]2 therefore implies steric contributions of the NHC ligands are the dominant factor. Figure 6.…”

Section: Effects Of Ligand Size Of Nhc and Electronic Properties Of Benzophenone Derivatives On The Rate Of Insertionmentioning

confidence: 99%

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

et al. 2020

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We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ‐H)]2 complexes with carbonyl substrates by UV‐vis and 1H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X‐ray crystallography. The results of these comprehensive studies show that the insertion of Cu‐H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu‐H monomer from Cu‐H dimer for more electrophilic substrates, and hydride transfer from a transient Cu‐H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu‐hemiacetalate and Cu‐hemiaminalate moieties from the insertion of an ester or amide into the Cu−H bond.

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Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides

Cited by 16 publications

References 115 publications

Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues

Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues

Synthesis and Reactivity of New Copper(I) Hydride Dimers

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

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Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides

Cited by 16 publications

References 115 publications

Hydrogenolysis of Dinuclear PCNR Ligated PdII μ‐Hydroxides and Their Mononuclear PdII Hydroxide Analogues

Hydrogenolysis of Dinuclear PCNR Ligated PdII μ‐Hydroxides and Their Mononuclear PdII Hydroxide Analogues

Synthesis and Reactivity of New Copper(I) Hydride Dimers

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

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Product

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Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues

Hydrogenolysis of Dinuclear PCN^R Ligated Pd^II μ‐Hydroxides and Their Mononuclear Pd^II Hydroxide Analogues