Nature of the hydrogen bridge in transition metal complexes

Jeżowska‐Trzebiatowska, B.; Nissen-Sobocińska, Barbara

doi:10.1016/s0022-328x(00)99459-2

Cited by 18 publications

(12 citation statements)

References 14 publications

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“…Compound 2 is also formally unsaturated and has a similarly short Re−Re distance, 2.876(1) Å. 4 Compound 2 also contains only 32 valence electrons and has been variously described as having no direct bonding between the two Re atoms, 28 A, a Re−Re single bond, D, or a Re−Re double bond, E. 4b Jeiowska-Trzebiatowska et al analyzed the electronic structure of 2 by using Fenske−Hall (FH) and extended Huckel (EH) methods. 28 King reported MPW1PW91 and BP86 geometryoptimized DFT calculations for 2.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…4 Compound 2 also contains only 32 valence electrons and has been variously described as having no direct bonding between the two Re atoms, 28 A, a Re−Re single bond, D, or a Re−Re double bond, E. 4b Jeiowska-Trzebiatowska et al analyzed the electronic structure of 2 by using Fenske−Hall (FH) and extended Huckel (EH) methods. 28 King reported MPW1PW91 and BP86 geometryoptimized DFT calculations for 2. 29 To investigate the nature of the Re−Re bonding in 1, we have performed geometry-optimized PBEsol DFT molecular orbital calculations.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

2013

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The compounds Re2(CO)8(μ-AuPPh3)2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV–vis radiation-induced decarbonylation of the compound Re(CO)5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re–Re bond distance in 1 is unusually short (Re–Re = 2.9070(3) Å), as found by a single-crystal structural analysis. The nature of the metal–metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO)8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ-AuPPh3)(μ-I), 3, and the known compound Re2(CO)8(μ-I)2, 4, by substitution of the bridging AuPPh3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re–Re single bond: Re–Re = 3.2067(5) Å. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CHCHC4H9) with Au(PPh3)I. The Re–Re bonding in compounds 3, 4, and Re2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

2013

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“…In the compound [Re 2 -(µ-H) 2 (CO) 8 ], which from electron counting rules formally has a M᎐ ᎐ M double bond, MO calculations have found no direct M-M bond leading to the suggestion that it is bonded exclusively through hydrogen bridges. 14 In order to account for the addition of this CO the metal to which it attaches may be bonded through a pair of hydride bridges and not by M-M bonding. Alternatively, the interaction can be viewed as a dative donor-acceptor bond, such interactions having been characterised in related systems.…”

Section: Resultsmentioning

confidence: 99%

Formation of the highly unusual cyclic clusters [MH(CO)4]n (M = Mn, n = 4–9; M = Re, n = 4–6) under laser desorption/ionisation conditions

Dyson

Hearley

Johnson

et al. 2000

J. Chem. Soc., Dalton Trans.

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The positive and negative ion ultraviolet laser desorption mass spectra of the trinuclear clusters [M 3 H 3 (CO) 12 ] (M = Mn 1 or Re 2) have been recorded using laser desorption/ionisation time-of-flight mass spectrometry (LDI-TOF-MS). The spectra contain peaks corresponding to trinuclear clusters together with peaks at higher masses arising from the series of condensed products [M n H n Ϫ 1 (CO) 4n ] Ϫ (where n = 4-9). These products are believed to have cyclic structures and to be formed by the stepwise insertion of [MH(CO) 4 ] into a metal-metal bond.

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“…[25] Alternatively, the [Re(m-H) 2 Re] system can be described as involving a pair of three-center, two-electron (3c-2e) bonds, [24a] and MO calculations [26] have found no direct metal ± metal bond in this system, leading to the suggestion that the metal atoms are bonded exclusively through the hydrogen bridges. From this point of view [Re 2 (m-H) 2 (CO) 8 ] is a close analogue of electron-deficient diborane, B 2 H 6 .…”

Section: The Unsaturated [Re 2 (M-h) 2 (Co) 8 ] Complex and Its Reactmentioning

confidence: 99%

Anionic Oligomerization as a Route to Chain Clusters

D’Alfonso

2000

Chem. Eur. J.

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The combination of two old concepts (the "sigma-donor" capability of M-H bonds and the propensity of unsaturated complexes for addition reactions) has led to the first example of addition oligomerization of an organometallic analogue of olefins: chains containing cis-[Re(CO)4] units joined by Re-H-Re interactions have been obtained through the oligomerization of the unsaturated complex [Re2(micro-H)2(CO)8] promoted by anionic "initiators". The limits of the method and the possible extension to other substrates are discussed.

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Nature of the hydrogen bridge in transition metal complexes

Cited by 18 publications

References 14 publications

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

Formation of the highly unusual cyclic clusters [MH(CO)4]n (M = Mn, n = 4–9; M = Re, n = 4–6) under laser desorption/ionisation conditions

Anionic Oligomerization as a Route to Chain Clusters

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