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Understanding the unexpected linearity of the trans-{Mn(NO) 2} 8 unit in a phthalocyanine complex: some thoughts on dinitrosylheme intermediates in biology
Simple MO arguments provide a qualitative explanation for the near-linear ON–Mn–NO arrangement observed for the trans-{Mn(NO) 2} 8 anion [Mn(Pc)(NO) 2] −, which is unexpected for an Enemark–Feltham electron count n > 6. The metal center in this species may be described as low-spin d 6 ( “ t 2 g 6...
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| Published in: | Journal of inorganic biochemistry 2005, Vol.99 (1), p.55-59 |
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| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
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| container_end_page | 59 |
| container_issue | 1 |
| container_start_page | 55 |
| container_title | Journal of inorganic biochemistry |
| container_volume | 99 |
| creator | Tangen, Espen Conradie, Jeanet Svadberg, Anders Ghosh, Abhik |
| description | Simple MO arguments provide a qualitative explanation for the near-linear ON–Mn–NO arrangement observed for the
trans-{Mn(NO)
2}
8 anion [Mn(Pc)(NO)
2]
−, which is unexpected for an Enemark–Feltham electron count
n
>
6. The metal center in this species may be described as low-spin
d
6
(
“
t
2
g
6
”
)
and the two unpaired electrons occupy a pair of e
u orbitals composed of NO(π*) components, giving rise to a triplet ground state. In a certain sense, these e
u SOMOs may be likened to the SOMO (singly occupied molecular orbital) of the allyl radical. The electronic structure of this species is quite different from that of diamagnetic dinitrosylheme intermediates, which have been spectroscopically characterized in synthetic studies as well as proposed for soluble guanylate cyclase and cytochrome
c′. Some speculative remarks are offered as to why this proposal is not an unreasonable one from an electronic-structural perspective. |
| doi_str_mv | 10.1016/j.jinorgbio.2004.10.010 |
| format | article |
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trans-{Mn(NO)
2}
8 anion [Mn(Pc)(NO)
2]
−, which is unexpected for an Enemark–Feltham electron count
n
>
6. The metal center in this species may be described as low-spin
d
6
(
“
t
2
g
6
”
)
and the two unpaired electrons occupy a pair of e
u orbitals composed of NO(π*) components, giving rise to a triplet ground state. In a certain sense, these e
u SOMOs may be likened to the SOMO (singly occupied molecular orbital) of the allyl radical. The electronic structure of this species is quite different from that of diamagnetic dinitrosylheme intermediates, which have been spectroscopically characterized in synthetic studies as well as proposed for soluble guanylate cyclase and cytochrome
c′. Some speculative remarks are offered as to why this proposal is not an unreasonable one from an electronic-structural perspective.</description><identifier>ISSN: 0162-0134</identifier><identifier>EISSN: 1873-3344</identifier><identifier>DOI: 10.1016/j.jinorgbio.2004.10.010</identifier><identifier>PMID: 15598491</identifier><language>eng</language><publisher>United States: Elsevier Inc</publisher><subject>Cytochrome c ; Dinitrosyl ; Dinitrosylheme ; Electrons ; Heme - chemistry ; Indoles - chemistry ; Manganese ; Manganese Compounds - chemistry ; Metals - chemistry ; Molecular Structure ; Nitrogen - chemistry ; Oxygen - chemistry ; Phthalocyanine ; Pigments, Biological - chemistry ; Soluble guanylate cyclase</subject><ispartof>Journal of inorganic biochemistry, 2005, Vol.99 (1), p.55-59</ispartof><rights>2004</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,4024,27923,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15598491$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Tangen, Espen</creatorcontrib><creatorcontrib>Conradie, Jeanet</creatorcontrib><creatorcontrib>Svadberg, Anders</creatorcontrib><creatorcontrib>Ghosh, Abhik</creatorcontrib><title>Understanding the unexpected linearity of the trans-{Mn(NO) 2} 8 unit in a phthalocyanine complex: some thoughts on dinitrosylheme intermediates in biology</title><title>Journal of inorganic biochemistry</title><addtitle>J Inorg Biochem</addtitle><description>Simple MO arguments provide a qualitative explanation for the near-linear ON–Mn–NO arrangement observed for the
trans-{Mn(NO)
2}
8 anion [Mn(Pc)(NO)
2]
−, which is unexpected for an Enemark–Feltham electron count
n
>
6. The metal center in this species may be described as low-spin
d
6
(
“
t
2
g
6
”
)
and the two unpaired electrons occupy a pair of e
u orbitals composed of NO(π*) components, giving rise to a triplet ground state. In a certain sense, these e
u SOMOs may be likened to the SOMO (singly occupied molecular orbital) of the allyl radical. The electronic structure of this species is quite different from that of diamagnetic dinitrosylheme intermediates, which have been spectroscopically characterized in synthetic studies as well as proposed for soluble guanylate cyclase and cytochrome
c′. Some speculative remarks are offered as to why this proposal is not an unreasonable one from an electronic-structural perspective.</description><subject>Cytochrome c</subject><subject>Dinitrosyl</subject><subject>Dinitrosylheme</subject><subject>Electrons</subject><subject>Heme - chemistry</subject><subject>Indoles - chemistry</subject><subject>Manganese</subject><subject>Manganese Compounds - chemistry</subject><subject>Metals - chemistry</subject><subject>Molecular Structure</subject><subject>Nitrogen - chemistry</subject><subject>Oxygen - chemistry</subject><subject>Phthalocyanine</subject><subject>Pigments, Biological - chemistry</subject><subject>Soluble guanylate cyclase</subject><issn>0162-0134</issn><issn>1873-3344</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNo9kctO3TAQhq2qVTmlfQXwqqKLHMaxc2OHEL1ItGxgbTnO5MRHiR1sBxFVfZK-bH0K7Wqk-b-5_oScMtgyYOX5frs31vlda9w2BxApuwUGr8iG1RXPOBfiNdkkMs-AcXFE3oWwB4CiENVbcsSKoqlFwzbk973t0IeobGfsjsYB6WLxaUYdsaOjsai8iSt1_V8temVD9vO7Pftx-4nmv2idcBOpsVTReYiDGp1elU11VLtpHvHpggY3pcrBLbshBuosTaNM9C6s44BJMjain7AzKmI4tEpXjW63vidvejUG_PASj8n95-u7q6_Zze2Xb1eXNxkylrNMQSlECW1dqU4rAN7kuqp4z1SBoBmWZS14pXuoGlRt2fAGhG46wXrR8rwo-DH5-Nx39u5hwRDlZILGcVQW3RJkWXHBS-AJPHkBlzbtK2dvJuVX-e-dCbh8BjCt-2jQy6ANWp1u8-mjsnNGMpAHC-Ve_rdQHiw8CMlC_getnJM3</recordid><startdate>2005</startdate><enddate>2005</enddate><creator>Tangen, Espen</creator><creator>Conradie, Jeanet</creator><creator>Svadberg, Anders</creator><creator>Ghosh, Abhik</creator><general>Elsevier Inc</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>2005</creationdate><title>Understanding the unexpected linearity of the trans-{Mn(NO) 2} 8 unit in a phthalocyanine complex: some thoughts on dinitrosylheme intermediates in biology</title><author>Tangen, Espen ; Conradie, Jeanet ; Svadberg, Anders ; Ghosh, Abhik</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-e1121-a064460b87adca00392c773f1a5e0c1e668437cf079eab693904c9d41f4b32553</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Cytochrome c</topic><topic>Dinitrosyl</topic><topic>Dinitrosylheme</topic><topic>Electrons</topic><topic>Heme - chemistry</topic><topic>Indoles - chemistry</topic><topic>Manganese</topic><topic>Manganese Compounds - chemistry</topic><topic>Metals - chemistry</topic><topic>Molecular Structure</topic><topic>Nitrogen - chemistry</topic><topic>Oxygen - chemistry</topic><topic>Phthalocyanine</topic><topic>Pigments, Biological - chemistry</topic><topic>Soluble guanylate cyclase</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tangen, Espen</creatorcontrib><creatorcontrib>Conradie, Jeanet</creatorcontrib><creatorcontrib>Svadberg, Anders</creatorcontrib><creatorcontrib>Ghosh, Abhik</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of inorganic biochemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tangen, Espen</au><au>Conradie, Jeanet</au><au>Svadberg, Anders</au><au>Ghosh, Abhik</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Understanding the unexpected linearity of the trans-{Mn(NO) 2} 8 unit in a phthalocyanine complex: some thoughts on dinitrosylheme intermediates in biology</atitle><jtitle>Journal of inorganic biochemistry</jtitle><addtitle>J Inorg Biochem</addtitle><date>2005</date><risdate>2005</risdate><volume>99</volume><issue>1</issue><spage>55</spage><epage>59</epage><pages>55-59</pages><issn>0162-0134</issn><eissn>1873-3344</eissn><abstract>Simple MO arguments provide a qualitative explanation for the near-linear ON–Mn–NO arrangement observed for the
trans-{Mn(NO)
2}
8 anion [Mn(Pc)(NO)
2]
−, which is unexpected for an Enemark–Feltham electron count
n
>
6. The metal center in this species may be described as low-spin
d
6
(
“
t
2
g
6
”
)
and the two unpaired electrons occupy a pair of e
u orbitals composed of NO(π*) components, giving rise to a triplet ground state. In a certain sense, these e
u SOMOs may be likened to the SOMO (singly occupied molecular orbital) of the allyl radical. The electronic structure of this species is quite different from that of diamagnetic dinitrosylheme intermediates, which have been spectroscopically characterized in synthetic studies as well as proposed for soluble guanylate cyclase and cytochrome
c′. Some speculative remarks are offered as to why this proposal is not an unreasonable one from an electronic-structural perspective.</abstract><cop>United States</cop><pub>Elsevier Inc</pub><pmid>15598491</pmid><doi>10.1016/j.jinorgbio.2004.10.010</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0162-0134 |
| ispartof | Journal of inorganic biochemistry, 2005, Vol.99 (1), p.55-59 |
| issn | 0162-0134 1873-3344 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_67343603 |
| source | Elsevier |
| subjects | Cytochrome c Dinitrosyl Dinitrosylheme Electrons Heme - chemistry Indoles - chemistry Manganese Manganese Compounds - chemistry Metals - chemistry Molecular Structure Nitrogen - chemistry Oxygen - chemistry Phthalocyanine Pigments, Biological - chemistry Soluble guanylate cyclase |
| title | Understanding the unexpected linearity of the trans-{Mn(NO) 2} 8 unit in a phthalocyanine complex: some thoughts on dinitrosylheme intermediates in biology |
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