Beryllium hydride explained

Beryllium hydride (systematically named poly[beryllane(2)] and beryllium dihydride) is an inorganic compound with the chemical formula (also written or). This alkaline earth hydride is a colourless solid that is insoluble in solvents that do not decompose it. Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded (three-center two-electron bond).

Synthesis

Unlike the other group 2 metals, beryllium does not react with hydrogen.[1] Instead, BeH is prepared from preformed beryllium(II) compounds. It was first synthesized in 1951 by treating dimethylberyllium, Be(CH), with lithium aluminium hydride, LiAlH.[2]

Purer BeH forms from the pyrolysis of di-tert-butylberyllium, Be(C[CH{{sub|3}}]) at 210°C.[3]

A route to highly pure samples involves the reaction of triphenylphosphine, PPh, with beryllium borohydride, Be(BH):

Be(BH) + 2 PPh → BeH + 2 PhPBH

Structure

Gaseous form

Isolated molecules of (sometimes called dihydridoberyllium and written to emphasize the differences with the solid state) are only stable as a dilute gas. When condensed, unsolvated will spontaneously autopolymerise.

Free molecular BeH produced by high-temperature electrical discharge has been confirmed to have linear geometry with a Be-H bond length of 133.376 pm. Its hybridization is sp.[4]

Condensed Beryllium hydride

BeH is usually formed as an amorphous white solid, but a hexagonal crystalline form with a higher density (~0.78 g/cm) was reported,[5] prepared by heating amorphous BeH under pressure, with 0.5-2.5% LiH as a catalyst.

A more recent investigation found that crystalline beryllium hydride has a body-centred orthorhombic unit cell, containing a network of corner-sharing BeH tetrahedra, in contrast to the flat, hydrogen-bridged, infinite chains previously thought to exist in crystalline BeH.[6]

Studies of the amorphous form also find that it consists of a network of corner shared tetrahedra.[7]

Chemical properties

Reaction with water and acids

Beryllium hydride reacts slowly with water but is rapidly hydrolysed by acid such as hydrogen chloride to form beryllium chloride.[1]

BeH + 2 HO → Be(OH) + 2 H

BeH + 2 HCl → BeCl + 2 H

Reaction with Lewis bases

The two-coordinate hydridoberyllium group can accept an electron-pair donating ligand (L) into the molecule by adduction:[8]

+ L → Because these reactions are energetically favored, beryllium hydride has Lewis-acidic character.

The reaction with lithium hydride (in which the hydride ion is the Lewis base), forms sequentially LiBeH and LiBeH. The latter contains the tetrahydridoberyllate(2-) anion .

Beryllium hydride reacts with trimethylamine, N(CH) to form a dimeric adduct with bridging hydrides.[9] However, with dimethylamine, HN(CH) it forms a trimeric beryllium diamide, [Be(N(CH{{sub|3}}){{sub|2}}){{sub|2}}], and hydrogen.

Notes and References

  1. Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier, p. 1048
  2. Glenn D. Barbaras . Clyde Dillard . A. E. Finholt . Thomas Wartik . K. E. Wilzbach . H. I. Schlesinger . amp . 1951 . The Preparation of the Hydrides of Zinc, Cadmium, Beryllium, Magnesium and Lithium by the Use of Lithium Aluminum Hydride . . 73 . 10 . 4585–4590 . 10.1021/ja01154a025 .
  3. G. E. Coates . F. Glockling . amp . 1954 . Di-tert.-butylberyllium and beryllium hydride . . 2526–2529 . 10.1039/JR9540002526.
  4. Peter F. Bernath . Alireza Shayesteh . Keith Tereszchuk . Reginald Colin . 2002 . The Vibration-Rotation Emission Spectrum of Free BeH2 . Science . 297 . 5585 . 1323–1324 . 2002Sci...297.1323B . 10.1126/science.1074580 . 12193780 . 40961746.
  5. G. J. Brendel . E. M. Marlett . L. M. Niebylski . amp . 1978 . Crystalline beryllium hydride . . 17 . 12 . 3589–3592 . 10.1021/ic50190a051.
  6. Gordon S. Smith . Quintin C. Johnson . Deane K. Smith. D. E. Cox . Robert L. Snyder . Rong-Sheng Zhou . Allan Zalkin . amp . 1988 . The crystal and molecular structure of beryllium hydride . . 67 . 5 . 491–494 . 10.1016/0038-1098(84)90168-6 . 1988SSCom..67..491S .
  7. Sujatha Sampath . Kristina M. Lantzky . Chris J. Benmore . Jörg Neuefeind . Joan E. Siewenie . amp . 2003 . Structural quantum isotope effects in amorphous beryllium hydride . J. Chem. Phys. . 119 . 23. 12499 . 10.1063/1.1626638. 2003JChPh.11912499S .
  8. Sharp . Stephanie B. . Gellene . Gregory I. . 23 November 2000 . σ Bond Activation by Cooperative Interaction with ns Atoms: Be + n, n = 1−3 . The Journal of Physical Chemistry A . 104 . 46 . 10951–10957 . 10.1021/jp002313m.
  9. Shepherd Jr.. Lawrence H. . Ter Haar, G. L. . Marlett, Everett M.. Amine complexes of beryllium hydride. Inorganic Chemistry. April 1969. 8. 4. 976–979. 10.1021/ic50074a051.