Synthesis and molecular structure of the niobocenecarbonylhydride adduct to bis(tetrahydroborate)zinc

Porai-Koshits, M. A.; Анцышкина, А. С.; Пасынский, А. А.; Садиков, Г. Г.; Skripkin, Yu.V.; Ostrikova, V.N.

doi:10.1016/s0020-1693(00)94661-9

Cited by 28 publications

(13 citation statements)

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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.…”

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confidence: 99%

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

2016

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“…The spectroscopic studies and CF analysis of Eu(C 5 H 11 COO) 3 Phen were reported previously by us [10]. The luminescence and luminescence excitation spectra have shown an efficient ligand-to-metal energy transfer and allow us describe its mechanism.…”

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confidence: 72%

“…The coordination polyhedron of lanthanide ion is close to the monocapped square antiprism. A relatively strong deviation of the respective C-C bonds of the capronate radical points at disordering of the structure, what is reflected in the temperature factors and can lead to a transformation of the structure with decrease of temperature [3].…”

Section: Resultsmentioning

confidence: 99%

“…Figs. 4 and 5 present the temperature dependence of the average experimental magnetic susceptibility χ M and χ M T measured between 1.9 and 300 K at 5000 G field for Eu(C 5 H 11 COO) 3 Phen and Nd(C 5 H 11 COO) 3 Phen, respectively. For Eu(III) compound the χ M T values decrease as temperature is lowered from 1.31 cm 3 mol −1 K (300.59 K) to 0.03 cm 3 mol −1 K (1.9 K).…”

Section: Resultsmentioning

confidence: 99%

“…[3]. The high-resolution absorption spectra at 293 and 4 K were recorded with CaryVarian 5 spectrophotometer equipped with an Oxford 1024 continuous helium cryostat.…”

Section: Methodsmentioning

confidence: 99%

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