Evidence for the Existence of a Potassium Rhenium Hydride and its Bearing on the Nature of the (−1)-Oxidation State of Rhenium

Ginsberg, A. P.; Miller, J.M.; Cavanaugh, Jack; Dailey, B. P.

doi:10.1038/185528a0

Cited by 13 publications

(3 citation statements)

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“…In 1947, Pauling suggested a structure of rhenide in which Re(−I) might bond with four water molecules to form a square-planar geometry because Re(−I) is isoelectronic with Pt(II) . The first solid rhenide, KRe·4H 2 O, was isolated by Kleinberg and co-workers using potassium metal as the reducing agent in aqueous ethylenediamine solution. , Shortly thereafter, Ginsberg and co-workers revealed that the solid rhenide is actually a soluble potassium rhenium hydride. − They also eliminated the possibility of the existence for rhenide by analyzing the UV absorption spectrum . Eventually, in 1964, almost 30 years after the discovery of rhenide, potassium rhenium hydride was structurally characterized as K 2 ReH 9 ( P 6̅2M space group) from X-ray crystallography and neutron diffraction studies. , …”

Section: Introductionmentioning

confidence: 99%

The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies

Agarwal

Schaefer

2014

J. Phys. Chem. B

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The equilibrium geometries and vibrational frequencies of the extraordinary [ReH9](2-) dianion (D3h symmetry) are investigated using Hartree-Fock (HF) theory, coupled cluster theory with single and double excitations (CCSD), and coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The new generation of energy-consistent relativistic pseudopotentials and correlation consistent basis sets [cc-pVXZ-PP (Re) and cc-pVXZ (H) (X = D, T, Q)] are used. Anharmonicity was considered using second-order vibrational perturbation theory. The predicted geometries and vibrational frequencies generally agree with experimental findings. In order to stabilize the [ReH9](2-) dianion, the M2ReH9 (M = Na, K) sandwich complexes (D3h symmetry) are studied at the CCSD(T)/VTZ (VTZ = cc-pVTZ-PP (Re) and cc-pVTZ (H, Na, K)) level of theory. Compared to the [ReH9](2-) dianion, the predicted vibrational frequencies involving Re-H stretching modes are improved, indicating the importance of considering counterions in electronically dense systems. The natural bond orbital analysis shows that each H atom only bonds with the Re center, and the 5d orbitals of Re and 1s orbitals of H are major factors for the covalent Re-H bonding.

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Section: Introductionmentioning

confidence: 99%

The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies

Agarwal

Schaefer

2014

J. Phys. Chem. B

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“…1959 berichteten dann Floss und Grosse u È ber die Reindarstellung von KRe´4 H 2 O [7]. 1960 zeigten Ginsberg, Miller, Cavanaugh und Dailey u È ber NMR-Messungen, daû Rhenium-Wasserstoff-Bindungen vorliegen [8]. Daraufhin wurde die Zusammensetzung mit der Formel KReH 4´2 H 2 O korrigiert [9].…”

Section: Introductionunclassified

K2ReH9, eine Neubestimmung der Struktur

Bronger¹,

Brassard²,

Müller³

et al. 1999

Z. anorg. allg. Chem.

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“…The structure of the homoleptic K 2 [ReH 9 ] and the correct oxidation state were determined in the 1960's by Abrahams and co‐workers via neutron diffraction clarifying the previously reported wrong assignment of four water molecules bound to the metal center (at first formulated as KRe · 4H 2 O) . Instead there were 9 hydrides bound to the rhenium as found by Ginsberg and co‐workers just 4 years earlier . Later Chart and Coffey prepared the stable [ReH 7 (PR 3 ) 2 ] complexes (R = PEt 2 Ph, PEtPh 2 or PPh 3 ) replacing two hydride ligands of the [ReH 9 ] 2– anion with two phosphines .…”

Section: Introductionmentioning

confidence: 66%

Solution and Solid‐State Structure of the First NHC‐Substituted Rhenium Heptahydrides

Grieco

Blacque²

2019

Eur J Inorg Chem

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The structure of three new bis(N‐heterocyclic carbene) heptahydride rhenium complexes ([ReH7(NHC)2] with NHC= IMes (2b) (1,3‐bis(2,4,6‐trimethyl phenyl) imidazol‐2‐ylidene), IMesCl2 (4b) (4,5‐dichloro‐1,3‐dihydro‐1,3‐bis(2,4,6‐trimethyl phenyl)‐2H‐imidazol‐2‐ylidene) BIMes (5b) (1,3‐Bis(2,4,6‐trimethylphenyl)‐benzo imidazole ylidene), and of the known complex [ReH7(PPh3)2] (1) (bis(triphenyl phosphine)‐rhenium heptahydride), and the one of their labelled counterparts 2c‐d7, 4c‐d7, and 5c‐d7, were established in solution. The compounds exchanged with HD (2 bar) at 60 °C in deuterated THF to produce statistically distributed isotopomers. This exchange pointed to the intermediacy of H2 complexes and dynamic systems with fast equilibration processes of all hydride positions. T1min measurements were run on 2b, 4b, 5b and 1 in deuterated methylcyclohexane: 2b T1min = 144 ms, 5b T1min = 127 ms, both at 203 K. For 4b two T1min values were obtained corresponding to the 1H‐NMR signals of the hydrides: T1min = 119 ms and T1min = 128 ms both at 203 K. The T1min values determined are typical of terminal rhenium polyhydrides and for 1 was reported a comparably short value of T1min (70 ms, [D8]toluene, at –73 °C), typical of complexes that contain dihydrogen ligands. D‐NMR T1min measurements were also run for the fully deuterated compounds 2c‐d7, 4c‐d7, 5c‐d7 and of 1c‐d7 allowing to calculate the ionicities of the metal hydride bonds. The Re‐D ionicity values were obtained from the Deuterium Quadrupole Coupling Constant (DQCC) determinations. They were in the range of 0.61–0.71 for the fully labelled complexes: 2c‐d7: T1min = 15 ms, i = 61 %; 4c‐d7: (A) T1min = 20 ms, i = 67 %, (B) T1min = 41 ms, i = 77 %; 5c‐d7: T1min = 24 ms, i= 70 %; and 1c‐d7: T1min = 26 ms, i = 71 %. Single crystal X‐ray diffraction studies on 4b enabled us to refine the hydride positions with only restraints in the bond lengths and thermal parameters. The X‐ray solid structure resembles a pseudo‐capped square antiprismatic geometry.

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Evidence for the Existence of a Potassium Rhenium Hydride and its Bearing on the Nature of the (−1)-Oxidation State of Rhenium

Cited by 13 publications

References 4 publications

The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies

The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies

K2ReH9, eine Neubestimmung der Struktur

Solution and Solid‐State Structure of the First NHC‐Substituted Rhenium Heptahydrides

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Evidence for the Existence of a Potassium Rhenium Hydride and its Bearing on the Nature of the (−1)-Oxidation State of Rhenium

Cited by 13 publications

References 4 publications

The Remarkable [ReH9]2– Dianion: Molecular Structure and Vibrational Frequencies

The Remarkable [ReH9]2– Dianion: Molecular Structure and Vibrational Frequencies

K2ReH9, eine Neubestimmung der Struktur

Solution and Solid‐State Structure of the First NHC‐Substituted Rhenium Heptahydrides

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The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies

The Remarkable [ReH₉]^2– Dianion: Molecular Structure and Vibrational Frequencies