Organoselenium Chemistry: Between Synthesis and Biochemistry

77Se NMR: Theoretical Aspects and Practical Applications

Author(s): Waro Nakanishi and Satoko Hayashi

Pp: 379-415 (37)

DOI: 10.2174/9781608058389114010016

* (Excluding Mailing and Handling)

Abstract

77Se NMR spectroscopy has been established as a powerful tool in the study of the selenium chemistry. 77Se NMR chemical shifts (δ(Se)) are sharply sensitive to the structural changes in selenium compounds. Therefore, they are widely applied to analyze the chemical bonds around Se atoms and to determine the structures. On the other hand, the calculated absolute magnetic shielding tensors of Se (σ(Se)) become much reliable. It is now possible to assign the spectra based not only on the empirical rules but also on the theoretical supports. Interpretation of the shift values separately by the contributions from the occupied orbitals and the orbital-orbital transitions is the typical example of the theoretical treatment. The theoretical background for the chemical shifts is explained, together with the coupling constants (J(Se, X)), although briefly. 77Se NMR spectra are measured on a daily basis and the structures of selenium compounds are determined through the assignment of the spectra. Applications of 77Se NMR are mainly discussed so as to give good hints when the spectra are assigned, for the better understanding of the selenium chemistry. Orientational effect on σ(Se) and δ(Se) by aryl groups, mechanisms for J(Se, X), NICS and relativistic effect on σ(Se) are also discussed, together with the usual applications.


Keywords: Relativistic effect, Ab initio calculations, Ligand effects, NMR spectroscopy, Selenium, Chemical shift, Spin-spin coupling, Isotopic effect, Natural bond orbital analysis, Structures.

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      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Trial Access" as access_base_text, CASE j.type WHEN 111 THEN true ELSE false END as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"chapter" as access_level, j.chapter_id from `user_access_chapter_trail` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 59068240 and j.to_ip >=59068240 )) and ((j.from_date <= 1739848428 and j.to_date >= 1739848428 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.chapter_id = 6310) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Subscribed" as access_base_text, false as terms_popup, "S" as content_download_type, null as restricted_user_access_key, null as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"chapter" as access_level, j.chapter_id from `user_access_chapter_corporate` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 59068240 and j.to_ip >=59068240 )) and ((j.from_date <= 1739848428 and j.to_date >= 1739848428 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.chapter_id = 6310) union (select j.user_access_id,j.volume_id,j.user_id,j.from_ip,j.to_ip,j.type,j.track,"Token Based Access" as access_base_text, false as terms_popup, "R" as content_download_type, j.uc_id as restricted_user_access_key, "v" as restricted_user_access_type, CASE j.track WHEN 0 THEN false ELSE true END as tracksAccessByVolume,"chapter" as access_level, j.chapter_id from `user_access_chapter_token` as `j` inner join `user_access_info` as `info` on `j`.`user_access_id` = `info`.`user_access_id` where ((j.from_ip <= 59068240 and j.to_ip >=59068240 )) and ((j.from_date <= 1739848428 and j.to_date >= 1739848428 and j.perpetual= 0) or (j.from_date is null and j.to_date is null and j.perpetual= 1)) and j.chapter_id = 6310)
      510μsalphaeurekaselec_live_10_06_2022UserAccess.php#1266
      Backtrace
      • 13. app/Models/UserAccess/UserAccess.php:1266
      • 14. app/Http/Controllers/ChapterController.php:1549
      • 15. vendor/laravel/framework/src/Illuminate/Routing/Controller.php:54
      • 16. vendor/laravel/framework/src/Illuminate/Routing/ControllerDispatcher.php:43
      • 17. vendor/laravel/framework/src/Illuminate/Routing/Route.php:260
    • select b.banner_link, b.banner_name, b.banner_script, b.banner_remarks, b.banner_file_name, b.banner_placement, bd.content_type, bd.content_id from `tbl_banner` as `b` inner join `tbl_banner_detail` as `bd` on `bd`.`banner_id` = `b`.`banner_id` inner join `users` as `u` on `u`.`id` = `b`.`updated_by` where `b`.`banner_ebook` = 1 and `bd`.`content_type` = 'B' and `bd`.`content_id` = 1492 and `b`.`banner_from_date` <= 1739848428 and `b`.`banner_to_date` >= 1739848428 and `b`.`banner_status` = 'A' order by `b`.`banner_id` desc
      1.13msalphaeurekaselec_live_10_06_2022Banner.php#95
      Bindings
      • 0: 1
      • 1: B
      • 2: 1492
      • 3: 1739848428
      • 4: 1739848428
      • 5: A
      Backtrace
      • 13. app/Models/Banner.php:95
      • 14. app/Http/helpers.php:404
      • 17. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 18. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    • select count(*) as aggregate from `uc_cart_products` where cart_id='91e700844d320e80692e396678fad507'
      250μsalphaeurekaselec_live_10_06_2022Cart.php#271
      Backtrace
      • 15. app/Models/Cart.php:271
      • 16. view::layouts._header:260
      • 18. vendor/laravel/framework/src/Illuminate/Filesystem/Filesystem.php:124
      • 19. vendor/laravel/framework/src/Illuminate/View/Engines/PhpEngine.php:58
      • 20. vendor/laravel/framework/src/Illuminate/View/Engines/CompilerEngine.php:73
    App\Models\Keywords
    10Keywords.php#?
    App\Models\Chapter
    1Chapter.php#?
    App\Models\Ebook
    1Ebook.php#?
        _token
        0UxmADuKUZ38MyD3GvGWRFNXO1pZBQgzIv41UN0g
        uc_cart_id
        91e700844d320e80692e396678fad507
        _previous
        array:1 [ "url" => "https://alpha.eurekaselect.com/chapter/6310" ]
        _flash
        array:2 [ "old" => [] "new" => [] ]
        PHPDEBUGBAR_STACK_DATA
        []
        path_info
        /chapter/6310
        status_code
        200
        
        status_text
        OK
        format
        html
        content_type
        text/html; charset=UTF-8
        request_query
        []
        
        request_request
        []
        
        request_headers
        0 of 0
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        request_cookies
        0 of 0
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        response_headers
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        ClearShow all
        Date ↕MethodURLData
        #12025-02-18 03:13:48GET/chapter/63101121912