[{ReH2(PMePh2)2}2(μ-H)3]-:  The First Member of a New Class of Anionic Polyhydride Dimers [Re2H7L4]-

Hinman, Justin G.; Abdur‐Rashid, Kamaluddin; Lough, and Alan J.; Morris, Robert H.

doi:10.1021/ic010041b

Cited by 18 publications

(15 citation statements)

References 22 publications

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“…Chemie appears in similarly bridged metal-hydride dimers of the composition [L 4 M À H 4 À ML 4 ]. [18] As the crystal lattices of 3-Lu and 4-Lu are similar, [19] hydrogenolysis of a single crystal of 3-Lu was performed to give 4-Lu with retention of the crystal morphology (Supporting Information).…”

Section: Methodsmentioning

confidence: 99%

Reversible Dihydrogen Activation in Cationic Rare‐Earth‐Metal Polyhydride Complexes

et al. 2013

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Dihydrogen activation by metal alkyl complexes via s-bond metathesis is a facile non-redox reaction and a common method for the preparation of rare-earth [1] and early-transition-metal hydrido complexes. [2] The intramolecular CÀH bond activation has been reported for metal alkyl or hydride complexes to give so-called "tucked-in" or "tucked-over" cyclometalated complexes with concomitant liberation of alkane or dihydrogen, [3] predominantly in metallocenes of early transition metals [2b, 4] and f-block elements. [5] The metallocene hydrides of zirconium [6] and samarium [5d] and tris-(amido) actinide hydrides [7] reversibly form the hydrido complex and the cyclometalated complexes by addition and removal of dihydrogen.We have reported a bimetallic trivalent rare-earth-metal complex with two bridging hydrido ligands that adds dihydrogen across a metal-carbon bond and a metal-metal axis. [8] The reverse liberation of dihydrogen by CÀH bond activation was not observed. [9] We have now obtained a rare-earth-metal hydrido complex capable of reversibly binding and releasing dihydrogen under mild conditions. No change in the oxidation state of the metals is involved, as addition and release occur by s-bond metathesis involving a metal-carbon bond. Notably, hydrogenolysis in the solid state was also observed in a single-crystal to single-crystal transformation.The cationic dialkyl lutetium complex [Lu(CH 2 SiMe 3 ) 2 -(thf) 3 ][A] (A = B{3,5-C 6 H 3 (CF 3 ) 2 } 4 ) [10] was treated with the neutral NNNN-type macrocyclic ligand 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me 4 TACD = Me 4 [12]aneN 4 ) to give the THF-free dialkyl complex [(Me 4 TACD)Lu-(CH 2 SiMe 3 ) 2 ][A] (1-Lu) in quantitative yield (Scheme 1). Scheme 1. CÀH bond activation in cationic bis(alkyl) complex 1-Lu to give complex 2-Lu.Scheme 2. Preparation of dicationic trihydrido complex 3-Lu.

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Section: Methodsmentioning

confidence: 99%

Reversible Dihydrogen Activation in Cationic Rare‐Earth‐Metal Polyhydride Complexes

et al. 2013

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“…In THF it is partially deprotonated by the base [PO(OEt) 2 NPh]to give a triply hydride bridged dirhenate complex, indicating that its pK a THF is 33 ( Figure 4). 144 Thus the two dirhenium complexes in Table 6 illustrate the dramatic change in acidity on going from carbonyl to phosphine ligation. The properties of several cationic polyhydride rhenium complexes have been reported (entries 18,22,[24][25][26][27].…”

Section: Figure 1 Reversible Protonation Of a Tungsten-tungsten Bondmentioning

confidence: 99%

Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes

2016

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Transition metal hydride complexes are usually amphoteric, not only acting as hydride donors, but also as Brønsted-Lowry acids. A simple additive ligand acidity constant equation (LAC for short) allows the estimation of the acid dissociation constant Ka(LAC) of diamagnetic transition metal hydride and dihydrogen complexes. It is remarkably successful in systematizing diverse reports of over 450 reactions of acids with metal complexes and bases with metal hydrides and dihydrogen complexes, including catalytic cycles where these reactions are proposed or observed. There are links between pKa(LAC) and pKa(THF), pKa(DCM), pKa(MeCN) for neutral and cationic acids. For the groups from chromium to nickel, tables are provided that order the acidity of metal hydride and dihydrogen complexes from most acidic (pKa(LAC) -18) to least acidic (pKa(LAC) 50). Figures are constructed showing metal acids above the solvent pKa scales and organic acids below to summarize a large amount of information. Acid-base features are analyzed for catalysts from chromium to gold for ionic hydrogenations, bifunctional catalysts for hydrogen oxidation and evolution electrocatalysis, H/D exchange, olefin hydrogenation and isomerization, hydrogenation of ketones, aldehydes, imines, and carbon dioxide, hydrogenases and their model complexes, and palladium catalysts with hydride intermediates.

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“…4; Tables 6 and 7). The isomers with one terminal H atom on each Re atom and three or four bridging [27][28][29][30][31] H atoms were considered for Cp 2 Re 2 H 6 . For example, the predicted isomer with one terminal H atom on each Re atom and four bridging H atoms has three imaginary frequencies (−389i cm −1 , −134i cm −1 , −46i cm −1 ) indicating the absence of the stationary points with this structure.…”

Section: Cp 2 Re 2 H 6 Structuresmentioning

confidence: 99%

Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands

Gao

King³

et al. 2015

J Mol Model

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Theoretical studies predict the lowest energy structures of the binuclear cyclopentadienylrhenium hydrides Cp2Re2H n (Cp = η(5)-C5H5; n = 4, 6, 8) to have a central doubly bridged Re2(μ-H)2 unit with terminal η(5)-Cp rings and the remaining hydrides as terminal ligands. However, the lowest energy Cp2Re2H2 structure by more than 12 kcal mol(-1) has one terminal η(5)-Cp ring, a bridging η(3),η(2)-Cp ring, and two terminal hydride ligands bonded to the same Re atom. The lowest energy hydride-free Cp2Re2 structure is a perpendicular structure with two bridging η(3),η(2)-Cp rings. The previously predicted bent singlet Cp2Re2 structure with terminal η(5)-Cp rings and a formal Re-Re sextuple bond lies ∼37 kcal mol(-1) above this lowest energy (η(3),η(2)-Cp)2Re2 structure. The thermochemistry of the CpReH n and Cp2Re2H n systems is consistent with the reported synthesis of the permethylated derivatives Cp*ReH6 and Cp*2Re2H6 (Cp* = η(5)-Me5C5) as very stable compounds. Additionally, natural bond orbital analysis, atoms-in-molecules and overlap population density-of-state in AOMIX were applied to present the existence of rhenium-rhenium multiple bonds.

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[{ReH₂(PMePh₂)₂}₂(μ-H)₃]^-: The First Member of a New Class of Anionic Polyhydride Dimers [Re₂H₇L₄]^-

Cited by 18 publications

References 22 publications

Reversible Dihydrogen Activation in Cationic Rare‐Earth‐Metal Polyhydride Complexes

Reversible Dihydrogen Activation in Cationic Rare‐Earth‐Metal Polyhydride Complexes

Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes

Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands

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