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Article: Synthesis of Bis(aliphatic amine)osmium(II), Bis(arylamido)osmium(IV), and Bis(imido)and Oxo(imido)osmium(VI) Porphyrins

TitleSynthesis of Bis(aliphatic amine)osmium(II), Bis(arylamido)osmium(IV), and Bis(imido)and Oxo(imido)osmium(VI) Porphyrins
Authors
Issue Date1997
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1997, v. 36 n. 14, p. 3064-3071 How to Cite?
AbstractThe syntheses, characterization, and reactivity of a series of osmium porphyrins, OsII(Por)(H2NR)2 [Por = dianions of octaethylporphyrinato (OEP), tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), mesotetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrinato (3,4,5-MeO-TPP). R = tBu; Por = TPP, R = iPr], OsII(Por)(HNEt2)2 (Por = TPP, 3,4,5-MeO-TPP), OsIV(Por)(NHAr)2 (Por = OEP, TPP, 3,4,5-MeO-TPP; Ar = Ph, 4-F-Ph). OsVI(Por)(NtBu)2 (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), OsVIO(Por)(NtBu) (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), and OsVIO(Por)(4-F-PhN) (Por = TPP, 3,4,5-MeO-TPP) are described. The complexes Os(Por)(HNAr)2 are prepared from the reactions of Os(Por)-(N2)(THF) with arylamines in aerobic tetrahydrofuran. Air oxidations of Os(Por)(H2NtBu)2 in tetrahydrofuran and in the presence of H2NtBu give OsO(Por)(NtBu) and Os(Por)(NtBu)2. The X-ray crystal structures of OsO-(TTP)(NtBu)·EtOH and Os(4-Cl-TPP)(NtBu)2 have been determined. Crystal data for OsO(TTP)(NtBu)·EtOH: monoclinic, space group P2l/c, a = 13.546(6) Å, b = 23.180(3) Å, c - 16.817(3) Å, β = 90.84(2)°, V = 5279.7-(1.0) Å3, Z = 4. Os(4-Cl-TPP)(NtBu)2: monoclinic, space group P2l/c, a = 11.046(2) Å. b = 18.380(3) Å, c = 23.640(4) Å, β= 97.22(1)°, V = 4759.8(1.0) Å, Z = 4. The Os=O and Os=NtBu distances in OsO(TTP)-(NtBu)·EtOH are 1.772(7) and 1.759(9) Å, respectively. The Os=NtBu distances in Os(4-Cl-TPP)(NtBu)2 average 1.775 Å. The imido angles range from 165.8(8) to 170.6(9)°. For the infrared spectra of these complexes, a discussion on the "oxidation state marker" band in the vicinity of 1000 cm-1 is presented. The differences in the electronic properties of osmium porphyrins at various oxidation states are also described.
Persistent Identifierhttp://hdl.handle.net/10722/69360
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLi, ZYen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:12:57Z-
dc.date.available2010-09-06T06:12:57Z-
dc.date.issued1997en_HK
dc.identifier.citationInorganic Chemistry, 1997, v. 36 n. 14, p. 3064-3071en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69360-
dc.description.abstractThe syntheses, characterization, and reactivity of a series of osmium porphyrins, OsII(Por)(H2NR)2 [Por = dianions of octaethylporphyrinato (OEP), tetraphenylporphyrinato (TPP), meso-tetrakis(p-tolyl)porphyrinato (TTP), mesotetrakis(4-chlorophenyl)porphyrinato (4-Cl-TPP), meso-tetrakis(3,4,5-trimethoxyphenyl)porphyrinato (3,4,5-MeO-TPP). R = tBu; Por = TPP, R = iPr], OsII(Por)(HNEt2)2 (Por = TPP, 3,4,5-MeO-TPP), OsIV(Por)(NHAr)2 (Por = OEP, TPP, 3,4,5-MeO-TPP; Ar = Ph, 4-F-Ph). OsVI(Por)(NtBu)2 (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), OsVIO(Por)(NtBu) (Por = TPP, TTP, 4-C1-TPP, 3,4,5-MeO-TPP), and OsVIO(Por)(4-F-PhN) (Por = TPP, 3,4,5-MeO-TPP) are described. The complexes Os(Por)(HNAr)2 are prepared from the reactions of Os(Por)-(N2)(THF) with arylamines in aerobic tetrahydrofuran. Air oxidations of Os(Por)(H2NtBu)2 in tetrahydrofuran and in the presence of H2NtBu give OsO(Por)(NtBu) and Os(Por)(NtBu)2. The X-ray crystal structures of OsO-(TTP)(NtBu)·EtOH and Os(4-Cl-TPP)(NtBu)2 have been determined. Crystal data for OsO(TTP)(NtBu)·EtOH: monoclinic, space group P2l/c, a = 13.546(6) Å, b = 23.180(3) Å, c - 16.817(3) Å, β = 90.84(2)°, V = 5279.7-(1.0) Å3, Z = 4. Os(4-Cl-TPP)(NtBu)2: monoclinic, space group P2l/c, a = 11.046(2) Å. b = 18.380(3) Å, c = 23.640(4) Å, β= 97.22(1)°, V = 4759.8(1.0) Å, Z = 4. The Os=O and Os=NtBu distances in OsO(TTP)-(NtBu)·EtOH are 1.772(7) and 1.759(9) Å, respectively. The Os=NtBu distances in Os(4-Cl-TPP)(NtBu)2 average 1.775 Å. The imido angles range from 165.8(8) to 170.6(9)°. For the infrared spectra of these complexes, a discussion on the "oxidation state marker" band in the vicinity of 1000 cm-1 is presented. The differences in the electronic properties of osmium porphyrins at various oxidation states are also described.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleSynthesis of Bis(aliphatic amine)osmium(II), Bis(arylamido)osmium(IV), and Bis(imido)and Oxo(imido)osmium(VI) Porphyrinsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=36&issue=14&spage=3064&epage=3071&date=1997&atitle=Synthesis+of+bis(aliphatic+amine)osmium(II),+bis(arylamido)osmium(IV)+and+bis(imido)-+and+oxo(imido)osmium(VI)porphyrinsen_HK
dc.identifier.emailHuang, JS:jshuang@hkucc.hku.hken_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic961228j-
dc.identifier.scopuseid_2-s2.0-0000241681en_HK
dc.identifier.hkuros27170en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000241681&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume36en_HK
dc.identifier.issue14en_HK
dc.identifier.spage3064en_HK
dc.identifier.epage3071en_HK
dc.identifier.isiWOS:A1997XH91600022-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLi, ZY=7409079858en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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