title: Impact of {Os(pap)2} in fine-tuning the binding modes and non-innocent potential of deprotonated 2,2'-bipyridine-3,3'-diol.
abstract: The reaction of ctc-Os(II)(pap)2Cl2 (pap = 2-phenylazopyridine, ctc = cis-trans-cis with respect to chlorides and pyridine/azo nitrogens of pap, respectively) and ambidentate 2,2'-bipyridine-3,3'-diol (H2L) leads to the simultaneous formation of isomeric [Os(II)(pap)2(HL(-))](+) ((2+)/(3+)), seven-membered chelate containing Os(II)(pap)2(L(2-)) (4) and diastereomeric [{Os(II)(pap)2}2(μ-L(2-))](2+) (5a(2+) (meso, ΔΛ)/5b(2+) (rac, ΔΔ/ΛΛ)). The reaction of 2,2'-biphenol (H2L') and ctc-Os(II)(pap)2Cl2 yields Os(II)(pap)2(L'(2-)) (6), an analogue of 4. The identities of the newly designed complexes have been established by different analytical, spectroscopic and X-ray diffraction techniques. (1)H-NMR spectra of the complexes and single crystal X-ray structures of selective derivatives [2]ClO4, [3]ClO4, [5a](ClO4)2, and 6 establish the retention of the tc-configuration of the precursor {Os(pap)2}. In isomeric 2(+) and 3(+), monodeprotonated HL(-) is linked to the {Os(II)(pap)2} fragment through N,N and N,O(-) donors, resulting in nearly planar five- and six-membered chelates with O-HO(-) and O-HN hydrogen bonds at its back face, respectively. The O(-),O(-) donating L'(2-) extends a severely twisted seven-membered chelate with the {Os(pap)2} unit in 6. The N,O(-)/O(-),N donors of deprotonated L(2-) bridge the two {Os(II)(pap)2} units in a symmetric fashion in 5a(2+), forming two moderately twisted six-membered chelates. Though the deprotonation of the O-HN hydrogen bond in (+) by another unit of {Os(II)(pap)2} generates a diastereomeric mixture of 5a(2+) and 5b(2+), attempts to deprotonate the relatively stronger O-H···O(-) hydrogen bond in 2(+) have failed. The isomeric 2(+)/3(+), seven-membered chelate containing 4/6 and diastereomeric 5a(2+)/5b(2+) exhibit distinctive (1)H-NMR and absorption spectra as well as electrochemical responses. The pap (N[double bond, length as m-dash]N) based two successive reductions and the participation of HL(-), L(2-), L'(2-) in the oxidation processes of the respective complexes have been revealed using EPR and DFT calculated MOs and Mulliken spin density plots at the intermediate paramagnetic states.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India. lahiri@chem.iitb.ac.in.
authors.forename: Prabir
authors.initials: P
authors.lastname: Ghosh
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India. lahiri@chem.iitb.ac.in.
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Lahiri