Structures of transition metal hydrides determined by neutron diffraction

Bau, Robert; Drabnis, Mary H.

doi:10.1016/s0020-1693(97)89125-6

Cited by 183 publications

(121 citation statements)

References 206 publications

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“…For this and other reasons, the reaction of hydrogen with soluble transition metal complexes has been extensively studied. The first molecular transition metal hydride complex to be reported was H 2 Fe(CO) 4 , described by Walter Hieber and coworkers in 1931. 1 In 1984, the first example of coordination of an intact dihydrogen molecule was reported by Greg Kubas and coworkers.…”

Section: Introductionmentioning

confidence: 99%

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Heinekey

2007

Labelled Comp Radiopharmac

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Complexation of dihydrogen to transition metal centers was discovered by Kubas and coworkers in 1984. The notion that the simplest molecule in chemistry can act as a ligand to form relatively stable transition metal complexes has led to a paradigm shift in coordination chemistry. Crucial to the exploration of this intriguing new chemistry has been the use of isotope substitution. Several aspects of the coordination chemistry of dihydrogen have revealed fascinating isotope effects on reactivity, spectroscopy and in some cases structure. Complexation of HD has been used to diagnose bond distances from measurements of J HD and isotope effects for D 2 versus H 2 binding have been evaluated. Examples of quantum mechanical exchange coupling in H 2 complexes have been described. These effects disappear when one of the H atoms is replaced by D. In molecules with bound hydrogen adjacent to a hydride ligand, non-statistical occupancy of hydrogen versus hydride sites by deuterons has been observed. In some cases, isotope-dependent structures have been established by the study of HD, HT and DT complexes using NMR spectroscopy.

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Section: Introductionmentioning

confidence: 99%

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Heinekey

2007

Labelled Comp Radiopharmac

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“…The Ru 3 Sb core is puckered because of the bridging hydrido ligand. As has already been well documented, [17] the hydrido-bridged RuRu bond [Ru1-Ru2 2.9748(2) Å] is significantly longer than the other two Ru-Ru bonds [Ru1-Ru3 2.8701(2) Å and Ru2-Ru3 2.84396(19) Å]. The differences in the bond parameters between 3 and its known osmium analogue 3-Os can be attributed to the different covalent radii of ruthenium and osmium.…”

Section: Synthesis and Reactivitymentioning

confidence: 61%

Synthesis and Reactivity of Ruthenium–Antimony Carbonyl Clusters

Ganguly

Leong

et al. 2015

Eur J Inorg Chem

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The reaction of Na[HRu3(CO)11] (2) with SbPh2Cl in dry tetrahydrofuran (THF) afforded the cluster Ru3(CO)10(μ‐H)(μ‐SbPh2) (3); in dry dichloromethane (DCM), the six‐membered ring Ru6(CO)20(μ‐H)2(μ‐SbPh2)2 (4) was obtained instead. The trimethylamine N‐oxide (TMNO) activated reaction of Ru3(CO)12 (1) with distibine Sb2Ph4 produced Ru3(CO)10(μ‐SbPh2)2 (6) through an Sb–Sb bond oxidative addition. Cluster 6 is fluxional through Ru–Ru bond isomerization. In contrast, its group 15 monosubstituted derivatives Ru3(CO)9(μ‐SbPh2)2(L) (7, L = phosphane, arsine or stibine) or the disubstituted derivatives Ru3(CO)8(μ‐SbPh2)2(L)2 (8) did not exhibit such fluxionality. Instead, isomerization through a turnstile mechanism involving the group 15 ligand occurred. The treatment of 6 with SbPh2Cl afforded the fused‐ring clusters Ru3(CO)9(μ‐SbPh2)3(Cl) (9) and Ru3(CO)8(μ‐SbPh2)3(Cl)(SbPh2CH2Cl) (10).

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“…[42] The d(W-H) values of 1.715 and 1.719 Å are close to the sum of the respective covalent radii [1.62 (Pauling) to 1.92 Å depending on values], [32] but the angle between the hydride ligands is only 66.4°, which renders their distance apart to only 1.84 Å. The QM/MM calculations reveal the dihydride to be significantly enthalpically favored (ΔH°= -17.3 kcal/mol; -13.0 kcal/mol from 2),but quite entropically disfavored (-40.0 eu; -24.1 eu from 2).…”

Section: Calculation Of Dihydrogen Addition Tomentioning

confidence: 94%

“…The base comprises the cyclometalated unit [O1-W1-C6 = 79.14(10)°], the two siloxy units adjacent [O1-W1-O2 = 102.92(9)°] to one another, and the methylene group opposing the siloxy oxygen atom, albeit with a rather small angle [(O2-W1-C2) = 129.98(10)°]; the hydride is likely to be in between, according to both its estimated position and calculations (vide infra). [27,[31][32][33][34][35] The W1-N1 bond length of 1.721(2) Å is typical for a high valent imido group, [36,37] and it is accompanied by a nearly linear W1-N1-C1 angle of Figure 2 illustrates the geometries of 1 and 2 obtained from ONIOM(M06:UFF) calculations. The geometry of pseudotrigonal 1 corresponds well with the structure obtained by X-ray crystallography, [29] and the T-shaped distortion is derived from the strong trans influence of the imido group, as described previously.…”

Section: Structure Ofmentioning

confidence: 99%

Lewis Bases Trigger Intramolecular CH–Bond Activation: (^tBu₃SiO)₂W=N^tBu [rlhar2] (^tBu₃SiO)(κO,κC‐^tBu₂SiOCMe₂CH₂)HW=N^tBu

et al. 2013

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The symmetry-forbidden cyclometalation of (silox) 2 /k D = 2.7(4)}, and equilibrium studies [ΔH°= -6.7(3) kcal/mol; ΔS°= -12.1(8) eu; ΔG°(25°C) = -3.1(4) kcal/mol]. The crystal structure of 2 reveals a pseudo-square-pyramidal structure that can be viewed as a distorted tetrahedron with the W-H and W-C bonds occupying one site. The addition of H 2 (or D 2 ) to 1 proceeds similarly to afford (silox) 2 ( t BuN=)WH 2 (3), and the addition of H 2 to 2

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Structures of transition metal hydrides determined by neutron diffraction

Cited by 183 publications

References 206 publications

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Synthesis and Reactivity of Ruthenium–Antimony Carbonyl Clusters

Lewis Bases Trigger Intramolecular CH–Bond Activation: (^tBu₃SiO)₂W=N^tBu [rlhar2] (^tBu₃SiO)(κO,κC‐^tBu₂SiOCMe₂CH₂)HW=N^tBu

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Structures of transition metal hydrides determined by neutron diffraction

Cited by 183 publications

References 206 publications

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Transition metal dihydrogen complexes: isotope effects on reactivity and structure

Synthesis and Reactivity of Ruthenium–Antimony Carbonyl Clusters

Lewis Bases Trigger Intramolecular CH–Bond Activation: (tBu3SiO)2W=NtBu [rlhar2] (tBu3SiO)(κO,κC‐tBu2SiOCMe2CH2)HW=NtBu

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Lewis Bases Trigger Intramolecular CH–Bond Activation: (^tBu₃SiO)₂W=N^tBu [rlhar2] (^tBu₃SiO)(κO,κC‐^tBu₂SiOCMe₂CH₂)HW=N^tBu