Divodonična veza

Divodonično vezivanje je evidentno u bliskim H---H kontaktima između kristalisane vode i borohidridnih anjona u soli NaBH4(H2O)2.[1]
Divodonično vezivanje se javlja između hidroksipiridina i hidridnog liganda u ovom kompleksu iridijuma.

Divodonična veza je vrsta vodonične veze, interakcije između veze metalnog hidrida i OH ili NH grupe, ili drugog protonskog donora. Sa van der Valsovim radijusom od 1,2 Å, atomi vodonika se obično ne približavaju drugim atomima vodonika na rastojanja manja od 2,4 Å. Prilazi bliži od 1,8 Å, su međutim karakteristični za divodonično vezivanje.[1]

Borni hidridi

Jedan od prvih primera ovog fenomenona su opisali Braun i Heseltin.[2] Oni su primetili intenzivnu apsorpciju u IR opsezima na 3300 i 3210 cm−1 rastvora (CH3)2NHBH3. Opseg više energije pripada normalnoj N−H vibraciji, dok opseg niže energije potiče od iste veze koja formira interakcije sa B−H. Nakon rastvaranja, 3300 cm−1 opseg povećava intenzited, a 3210 cm−1 opseg se umanjuje, usled intermolekularnih asocijacija.

Interest u divodonično vezivanje je oživeo nakon kristalografske karakterizacije molekula H3NBH3. U ovom molekulu, poput molekula koji su izučavali Braun i Hazeltin, atomi vodonika na azotu imaju parcijalno pozitivno naelektrisanje, Hδ+, a atomi vodonika na boru parcijalno negativno naelektrisanje, Hδ−.[3] Rezultujuće B−H...H−N privlačenje stabilizuje molekul u čvrstom stanju. U kontrastu s tim, srodna supstanca etan, H3CCH3, je gas sa tačkom klučanja nižom od 285 °C. Pošto učestvuju dva vodonična centra, interakcija se naziva divodonična veza.

Smatra se da dolazi do formiranja divodonične veze pre formiranja H2 u reakciji hidrida i protinske kiseline. Veoma kratke divodonične veze su primećena u NaBH4·2H2O sa H−H kontaktima od 1,79, 1,86 i 1,94 Å.[1]

Koordinaciona hemija

Smatra se da do protonacije hidridnih kompleksa prelaznih metala generalno dolazi putem divodoničnog vezivanja.[4] Ova vrsta H−H interakcija se razlikuje od H−H} vezivanja kod kompleksa prelaznih metala koji imaju divodoničnu vezu sa metalom.[5][6]

Reference

  1. ↑ 1,0 1,1 1,2 Custelcean, Radu; James E. Jackson (2001-07-01). „Dihydrogen Bonding: Structures, Energetics, and Dynamics”. Chemical Reviews 101 (7): 1963–1980. DOI:10.1021/cr000021b. PMID 11710237. 
  2. ↑ Brown, M. P.; R. W. Heseltine (1968). „Co-ordinated BH3 as a proton acceptor group in hydrogen bonding”. Chemical Communications (London) (23): 1551–1552. DOI:10.1039/C19680001551. 
  3. ↑ Crabtree, Robert H.; Per E. M. Siegbahn, Odile Eisenstein, Arnold L. Rheingold, Thomas F. Koetzle (1996-01-01). „A New Intermolecular Interaction: Unconventional Hydrogen Bonds with Element−Hydride Bonds as Proton Acceptor”. Accounts of Chemical Research 29 (7): 348–354. DOI:10.1021/ar950150s. PMID 19904922. 
  4. ↑ Natalia V. Belkova, Elena S. Shubina, and Lina M. Epstein "Diverse World of Unconventional Hydrogen Bonds" Acc. Chem. Res., 2005, vol. 38, pp 624–631 DOI:10.1021/ar040006j
  5. ↑ Kubas, Gregory J. (31. 8. 2001.). Metal Dihydrogen and -Bond Complexes - Structure, Theory, and Reactivity (1 izd.). Springer. ISBN 0-306-46465-9. 
  6. ↑ Bakhmutov, Vladimir. I. (2008). Dihydrogen bonds: Principles, Experiments and Applications. Hoboken, Nj,: John Wiley & Sons, Inc.. ISBN 9780470180969. 

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