Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(ii) complexes

Simon K. Brayshaw; Timothy L. Easun; Michael W. George; Alexandra M.E. Griffin; Andrew L. Johnson; Paul R. Raithby; Teresa L. Savarese; Stefanie Schiffers; John E. Warren; Mark R. Warren; Simon J. Teat

doi:10.1039/c1dt11379h

Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(ii) complexes

Simon K. Brayshaw, Timothy L. Easun, Michael W. George, Alexandra M.E. Griffin, Andrew L. Johnson, Paul R. Raithby, Teresa L. Savarese, Stefanie Schiffers, John E. Warren, Mark R. Warren, Simon J. Teat

Research output: Journal Publication › Article › peer-review

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Abstract

Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(ii) nitrito complexes [Ni(aep)₂(η ¹-ONO)₂] 1#O (aep = 1-(2-aminoethyl)piperidine), [Ni(aem)₂(η¹-ONO)₂] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)₂(η¹-ONO) ₂] 3#O (aepy = 1-(2-aminoethyl)pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)₂(η¹-NO ₂)₂] 1, [Ni(aem)₂(η¹-NO ₂)₂] 2 and [Ni(aepy)₂(η¹-NO ₂)₂] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.

Original language	English
Pages (from-to)	90-97
Number of pages	8
Journal	Dalton Transactions
Volume	41
Issue number	1
DOIs	https://doi.org/10.1039/c1dt11379h
Publication status	Published - 7 Jan 2012
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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@article{2fe1a601627f4bfcb05db463575a6269,

title = "Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(ii) complexes",

abstract = "Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(ii) nitrito complexes [Ni(aep)2(η 1-ONO)2] 1#O (aep = 1-(2-aminoethyl)piperidine), [Ni(aem)2(η1-ONO)2] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)2(η1-ONO) 2] 3#O (aepy = 1-(2-aminoethyl)pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)2(η1-NO 2)2] 1, [Ni(aem)2(η1-NO 2)2] 2 and [Ni(aepy)2(η1-NO 2)2] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.",

author = "Brayshaw, {Simon K.} and Easun, {Timothy L.} and George, {Michael W.} and Griffin, {Alexandra M.E.} and Johnson, {Andrew L.} and Raithby, {Paul R.} and Savarese, {Teresa L.} and Stefanie Schiffers and Warren, {John E.} and Warren, {Mark R.} and Teat, {Simon J.}",

year = "2012",

month = jan,

day = "7",

doi = "10.1039/c1dt11379h",

language = "English",

volume = "41",

pages = "90--97",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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T1 - Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(ii) complexes

AU - Brayshaw, Simon K.

AU - Easun, Timothy L.

AU - George, Michael W.

AU - Griffin, Alexandra M.E.

AU - Johnson, Andrew L.

AU - Raithby, Paul R.

AU - Savarese, Teresa L.

AU - Schiffers, Stefanie

AU - Warren, John E.

AU - Warren, Mark R.

AU - Teat, Simon J.

PY - 2012/1/7

Y1 - 2012/1/7

N2 - Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(ii) nitrito complexes [Ni(aep)2(η 1-ONO)2] 1#O (aep = 1-(2-aminoethyl)piperidine), [Ni(aem)2(η1-ONO)2] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)2(η1-ONO) 2] 3#O (aepy = 1-(2-aminoethyl)pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)2(η1-NO 2)2] 1, [Ni(aem)2(η1-NO 2)2] 2 and [Ni(aepy)2(η1-NO 2)2] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.

AB - Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(ii) nitrito complexes [Ni(aep)2(η 1-ONO)2] 1#O (aep = 1-(2-aminoethyl)piperidine), [Ni(aem)2(η1-ONO)2] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)2(η1-ONO) 2] 3#O (aepy = 1-(2-aminoethyl)pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)2(η1-NO 2)2] 1, [Ni(aem)2(η1-NO 2)2] 2 and [Ni(aepy)2(η1-NO 2)2] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.

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Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(ii) complexes

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