Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)
Reaction of (μ-bpym)RuCl(terpy)2(PF6)2, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2''-terpyridine, with NaNO2 yields (μ-bpym)Ru(NO2)(terpy)2(PF6)2. In CH3CN/0.1 M Bu4NPF6 both dinuclear complexes can undergo two reversible bpym-centered 1-electron redn. processes and two metal-centered 1-electron oxidn. steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of (μ-bpym)Ru(NO2)(terpy)2(PF6)2 does not lead to the expected (μ-bpym)Ru(NO)(terpy)26+ but, probably because of the high charge, to the insol. but structurally and IR-spectroscopically characterized pseudo-base product syn-(μ-bpym-(4-OH))Ru(NO)(terpy)2(PF6)5. The addn. of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the arom. p conjugation and is accompanied by corresponding intra-pyrimidine bond length variations, however, the effect on the electronic interaction of the two different syn positioned RuNO6 moieties remains small, possibly due to their situation within the central mol. p plane. on SciFinder(R)
%0 Journal Article
%1 Singh.2008
%A Singh, Priti
%A Sieger, Monika
%A Fiedler, Jan
%A Su, Cheng-Yong
%A Kaim, Wolfgang.
%D 2008
%J Dalton Transactions
%K bipyrimidine complex complex;ruthenium crystal dinuclear hydroxybipyrimidine nitrosyl prepn ruthenium spectroelectrochem structure terpyridine
%N 7
%P 868--873
%R 10.1039/B716307J
%T Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)
%X Reaction of (μ-bpym)RuCl(terpy)2(PF6)2, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2''-terpyridine, with NaNO2 yields (μ-bpym)Ru(NO2)(terpy)2(PF6)2. In CH3CN/0.1 M Bu4NPF6 both dinuclear complexes can undergo two reversible bpym-centered 1-electron redn. processes and two metal-centered 1-electron oxidn. steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of (μ-bpym)Ru(NO2)(terpy)2(PF6)2 does not lead to the expected (μ-bpym)Ru(NO)(terpy)26+ but, probably because of the high charge, to the insol. but structurally and IR-spectroscopically characterized pseudo-base product syn-(μ-bpym-(4-OH))Ru(NO)(terpy)2(PF6)5. The addn. of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the arom. p conjugation and is accompanied by corresponding intra-pyrimidine bond length variations, however, the effect on the electronic interaction of the two different syn positioned RuNO6 moieties remains small, possibly due to their situation within the central mol. p plane. on SciFinder(R)
@article{Singh.2008,
abstract = {Reaction of {(μ-bpym)[RuCl(terpy)]2}(PF6)2, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2''-terpyridine, with NaNO2 yields {(μ-bpym)[Ru(NO2)(terpy)]2}(PF6)2. In CH3CN/0.1 M Bu4NPF6 both dinuclear complexes can undergo two reversible bpym-centered 1-electron redn. processes and two metal-centered 1-electron oxidn. steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of {(μ-bpym)[Ru(NO2)(terpy)]2}(PF6)2 does not lead to the expected {(μ-bpym)[Ru(NO)(terpy)]2}6+ but, probably because of the high charge, to the insol. but structurally and IR-spectroscopically characterized pseudo-base product syn-{(μ-bpym-(4-OH))[Ru(NO)(terpy)]2}(PF6)5. The addn. of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the arom. \textgreek{p} conjugation and is accompanied by corresponding intra-pyrimidine bond length variations, however, the effect on the electronic interaction of the two different syn positioned {RuNO}6 moieties remains small, possibly due to their situation within the central mol. \textgreek{p} plane. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Singh, Priti and Sieger, Monika and Fiedler, Jan and Su, Cheng-Yong and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/20116fed06caede518300ac493c5b416a/b_schwederski},
doi = {10.1039/B716307J},
interhash = {79d2eddc53f24343be4648d5f6d0bd45},
intrahash = {0116fed06caede518300ac493c5b416a},
issn = {1477-9226},
journal = {Dalton Transactions},
keywords = {bipyrimidine complex complex;ruthenium crystal dinuclear hydroxybipyrimidine nitrosyl prepn ruthenium spectroelectrochem structure terpyridine},
number = 7,
pages = {868--873},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)},
year = 2008
}
