Dinuclear elimination from rhenium hydrides and trimethylaluminum: rhenium/aluminum polyhydrides

Skupiński, Wincenty; Huffman, John C.; Bruno, Joseph W.; Caulton, Kenneth G.

doi:10.1021/ja00338a021

Cited by 45 publications

(28 citation statements)

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“…Solvents were purged with a nitrogen flow before use. The ReCl 3 (PMePh 2 ) 3 complex, 21 2-ethynylbenzonitrile, 22 and 2-ethynyl-5-trifluoromethylbenzonitrile 23 were prepared according to literature methods. The other reagents were used as purchased.…”

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confidence: 99%

Synthesis, structure and aromaticity of metallapyridinium complexes

et al. 2022

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Section: General Informationmentioning

confidence: 99%

Synthesis, structure and aromaticity of metallapyridinium complexes

et al. 2022

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“…The main group fragment of 98 and 99 is {AlMe 2 } + , which may exchange between different positions on the face of the {P 3 ReH 4 } – and {P 2 ReH 6 } – polyhedra. 172 For comparison, [ReH 9 ] 2– is well-known as the dipotassium salt. 173 …”

Section: Multiply-bridged Complexes (Tm–h N –Mmentioning

confidence: 99%

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Butler

Crimmin

2017

Chem. Commun.

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“…[5] The proposition that these species could dimerize by 3-center 2-electron bonds seeded ideas that ultimately led to the discovery of dihydrogen complexes. [6] A handful of heterobimetallic complexes containing transition metal and zinc centers bridged by hydride ligands are known, [7][8][9][10][11][12][13][14] The majority however, include more than one bridging hydride ligand clouding analysis of the TM-H-Zn group. Through kinetic protection of a zinc center with a sterically demanding ligand, we recently isolated a rare example of a heterobimetallic complex possessing an unsupported Cu-H-Zn moiety.…”

Section: Abstract: Through a Dramatic Advance In The Coordination Chementioning

confidence: 99%

“…[6] Ah andful of heterobimetallic complexes containing transition metal and zinc centers bridged by hydride ligands are known. [7][8][9][10][11][12][13][14][15] Themajority however, include more than one bridging hydride ligand clouding analysis of the TM-H-Zn group.T hrough kinetic protection of az inc center with asterically demanding ligand, we recently isolated ar are example of ah eterobimetallic complex possessing an unsupported Cu-H-Zn moiety. [15c] Here we describe an advance in the coordination chemistry of the zinc-hydride bond to transition metals.Through analysis of aseries of solid state structures and calculations,w ed escribe the reaction trajectory for the approach of as ingle zinc-hydride bond to atransition metal.…”

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Trajectory of Approach of a Zinc–Hydrogen Bond to Transition Metals

2016

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Through a dramatic advance in the coordination chemistry of the zinc-hydride bond, we describe the trajectory for the approach of this bond to transition metals. The dynamic reaction coordinate was interrogated through analysis of a series of solid state structures and is one in which the TM-H-Zn angle becomes increasingly acute as the TM---Zn distance decreases. Parallels may be drawn with the oxidative addition of boron-hydrogen and silicon-hydrogen bonds to transition metal centers.Appreciation of the trajectory for the approach of carbon-hydrogen bonds to transition metals has led to a deeper understanding of catalytic processes involving the breaking of carbon-hydrogen bonds. [1] As the C-H bond advances towards the metal, formation of an intermediate σ-complex can preface oxidative addition. [2] Many authors have described a continuum between the σ-complex and oxidative addition product. [2][3] As the M---C distance decreases, the H-M-C angle becomes increasingly acute and electron density is transferred from both the d-orbitals of the metal and breaking C-H bond to the forming M-C and M-H bonds. Alkanes are not privileged in this regard, σ-borane and σ-silane complexes have an extensive chemistry and the relationship between them and the oxidative addition products metal boryls and metal silyls is well understood (Figure 1). [4] In comparison there is only limited precedent for the coordination of zinc hydrides to transition metal centers. Kubas and Shriver have commented on the nature of hydride-bridged zincate complexes in solution. [5] The proposition that these species could dimerize by 3-center 2-electron bonds seeded ideas that ultimately led to the discovery of dihydrogen complexes. [6] A handful of heterobimetallic complexes containing transition metal and zinc centers bridged by hydride ligands are known, [7][8][9][10][11][12][13][14] The majority however, include more than one bridging hydride ligand clouding analysis of the TM-H-Zn group. Through kinetic protection of a zinc center with a sterically demanding ligand, we recently isolated a rare example of a heterobimetallic complex possessing an unsupported Cu-H-Zn moiety. [15] Here we describe an advance in the coordination chemistry of the zinc hydride bond to transition metals. Through analysis of a series of solid state structures and calculations, we describe the reaction trajectory for the approach of a single zinc-hydride bond to a transition metal.Photolysis . While a similar protocol could not be used to synthesize the tungsten pentacarbonyl complex 2c, photolysis of [W(CO)6] in d8-THF for 6h followed by addition of 1 gave the desired product. The rhodium complex 5b was prepared by in situ generation of [Cp*Rh(H)2(SiEt3)(ZnBDI)] (5a) [10a] followed by photolysis in the presence of excess PMe3 (BDI = {2,6-i Pr2C6H3NCMe}2CH). A series of increasingly electron-rich ligands were included on the transition metal fragments to allow variation of the electron density at the TM center.The new heterobimetallic complexes 2-5 poss...

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Dinuclear elimination from rhenium hydrides and trimethylaluminum: rhenium/aluminum polyhydrides

Cited by 45 publications

References 2 publications

Synthesis, structure and aromaticity of metallapyridinium complexes

Synthesis, structure and aromaticity of metallapyridinium complexes

Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals

Trajectory of Approach of a Zinc–Hydrogen Bond to Transition Metals

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