PMID- 21355612
OWN - NLM
STAT- MEDLINE
DCOM- 20110711
LR  - 20131121
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 50
IP  - 7
DP  - 2011 Apr 4
TI  - Structural, electronic, and acid/base properties of [Ru(bpy)2(bpy(OH)2)]2+ (bpy = 
      2,2'-bipyridine, bpy(OH)2 = 4,4'-dihydroxy-2,2'-bipyridine).
PG  - 2754-63
LID - 10.1021/ic1017054 [doi]
AB  - We have synthesized the complex [Ru(bpy)(2)(bpy(OH)(2))](2+) (bpy 
      =2,2'-bipyridine, bpy(OH)(2) = 4,4'-dihydroxy-2,2'-bipyridine). Experimental 
      results coupled with computational studies were utilized to investigate the 
      structural and electronic properties of the complex, with particular attention 
      paid toward the effects of deprotonation on these properties. The most 
      distinguishing feature observed in the X-ray structural data is a shortening of 
      the CO bond lengths in the modified ligand upon deprotonation. Similar results 
      are also observed in the computational studies as the CO bond becomes double bond 
      in character after deprotonating the complex. Electrochemically, the 
      hydroxy-modified bipyridyl ligand plays a significant role in the redox 
      properties of the complex. When protonated, the bpy(OH)(2) ligand undergoes 
      irreversible reduction processes; however, when deprotonated, reduction of the 
      substituted ligand is no longer observed, and several new irreversible oxidation 
      processes associated with the modified ligand arise. pH studies indicate 
      [Ru(bpy)(2)(bpy(OH)(2))](2+) has two distinct deprotonations at pK(a1) = 2.7 and 
      pK(a2) = 5.8. The protonated [Ru(bpy)(2)(bpy(OH)(2))](2+) complex has a 
      characteristic UV/Visible absorption spectrum similar to the well-studied complex 
      [Ru(bpy)(3)](2+) with bands arising from Metal-to-Ligand Charge Transfer (MLCT) 
      transitions. When the complex is deprotonated, the absorption spectrum is altered 
      significantly and becomes heavily solvent dependent. Computational methods 
      indicate that the deprotonated bpy(O(-))(2) ligand mixes heavily with the metal d 
      orbitals leading to a new absorption manifold. The transitions in the complex 
      have been assigned as mixed Metal-Ligand to Ligand Charge Transfer (MLLCT).
FAU - Klein, Samantha
AU  - Klein S
AD  - Department of Chemistry, Villanova University, Villanova, Pennsylvania 19085, 
      USA.
FAU - Dougherty, William G
AU  - Dougherty WG
FAU - Kassel, W Scott
AU  - Kassel WS
FAU - Dudley, Timothy J
AU  - Dudley TJ
FAU - Paul, Jared J
AU  - Paul JJ
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20110228
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (Coordination Complexes)
RN  - 7UI0TKC3U5 (Ruthenium)
SB  - IM
EIN - Inorg Chem. 2013 Jan 7;52(1):528
MH  - Coordination Complexes/*chemistry
MH  - Crystallography, X-Ray
MH  - *Electrons
MH  - Models, Molecular
MH  - Molecular Structure
MH  - Ruthenium/*chemistry
EDAT- 2011/03/02 06:00
MHDA- 2011/07/12 06:00
CRDT- 2011/03/02 06:00
PHST- 2011/03/02 06:00 [entrez]
PHST- 2011/03/02 06:00 [pubmed]
PHST- 2011/07/12 06:00 [medline]
AID - 10.1021/ic1017054 [doi]
PST - ppublish
SO  - Inorg Chem. 2011 Apr 4;50(7):2754-63. doi: 10.1021/ic1017054. Epub 2011 Feb 28.