TY - JOUR
T1 - Dimolybdenum bis-2,4,6-triisopropyl-benzoate bis-4-isonicotinate
T2 - A redox active analogue of 4,4′-bipyridine with ambivalent properties
AU - Chisholm, Malcolm H.
AU - Dann, Angela S.
AU - Dielmann, Fabian
AU - Gallucci, Judith C.
AU - Patmore, Nathan J.
AU - Ramnauth, Ramkrishna
AU - Scheer, Manfred
PY - 2008/10/20
Y1 - 2008/10/20
N2 - The reaction between Mo2(TiPB)4 and 4-iso-nicotinic acid (2 equiv) in ethanol leads to the formation of trans-Mo2(TiPB) 2(nic)2, I, where TiPB = 2,4,6-triisopropylbenzoate and nic = 4-isonicotinate. The molecular structures of I and I·2DMSO were determined in the solid state by a single-crystal X-ray study, and its electronic structure was determined by DFT calculations on a model compound, where formate ligands were substituted for the bulky TiPB. The physicochemical properties of I are reported, and its potential as a redox active building block, a quasimetalloorganic analogue of 4,4′-bipyridine, is described in the synthesis of molecular and solid-state assemblies. The molecular structure of I in the solid state consists of a 3-dimensional network in which each unit of Mo2(TiPB)2(nic)2 acts as a donor and acceptor via N to Mo coordination. In the structure of I·2DMSO, the DMSO ligands coordinate axially with the Mo-Mo bond via oxygen. The reaction between I and Rh2(O2CMe)4 is shown to give a 1-D polymeric chain in the solid state: [{Rh2(O2CMe) 4}{Mo2(TiPB)2(nic)2}] ∞, II. A similar structure was found for the product involving Rh2(O2CCMe3)4. Evidence is also reported for the formation of [(1,5-COD)MePt]2[μ-Mo 2(TiPB)2(nic)2](PF6)2, III, and [(1,5-COD)Pt(μ-I)(PF6)2]n.
AB - The reaction between Mo2(TiPB)4 and 4-iso-nicotinic acid (2 equiv) in ethanol leads to the formation of trans-Mo2(TiPB) 2(nic)2, I, where TiPB = 2,4,6-triisopropylbenzoate and nic = 4-isonicotinate. The molecular structures of I and I·2DMSO were determined in the solid state by a single-crystal X-ray study, and its electronic structure was determined by DFT calculations on a model compound, where formate ligands were substituted for the bulky TiPB. The physicochemical properties of I are reported, and its potential as a redox active building block, a quasimetalloorganic analogue of 4,4′-bipyridine, is described in the synthesis of molecular and solid-state assemblies. The molecular structure of I in the solid state consists of a 3-dimensional network in which each unit of Mo2(TiPB)2(nic)2 acts as a donor and acceptor via N to Mo coordination. In the structure of I·2DMSO, the DMSO ligands coordinate axially with the Mo-Mo bond via oxygen. The reaction between I and Rh2(O2CMe)4 is shown to give a 1-D polymeric chain in the solid state: [{Rh2(O2CMe) 4}{Mo2(TiPB)2(nic)2}] ∞, II. A similar structure was found for the product involving Rh2(O2CCMe3)4. Evidence is also reported for the formation of [(1,5-COD)MePt]2[μ-Mo 2(TiPB)2(nic)2](PF6)2, III, and [(1,5-COD)Pt(μ-I)(PF6)2]n.
UR - http://www.scopus.com/inward/record.url?scp=55249120038&partnerID=8YFLogxK
U2 - 10.1021/ic800693r
DO - 10.1021/ic800693r
M3 - Article
AN - SCOPUS:55249120038
VL - 47
SP - 9248
EP - 9255
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 20
ER -