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Synthesis and Structural Studies of Pyridine‐2‐selenolates − Reactions with Electrophilic Phosphorus(III) Compounds and Related Complex Chemistry
Author(s) -
Laube Jörg,
Jäger Stefan,
Thöne Carsten
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200108)2001:8<1983::aid-ejic1983>3.0.co;2-w
Subject(s) - chemistry , tetrahydrothiophene , pyridine , electrophile , crystal structure , medicinal chemistry , diselenide , square pyramid , tautomer , stereochemistry , crystallography , selenium , organic chemistry , catalysis
The reaction intermediates in the synthesis of 2,2′‐bis(pyridyl) diselenide (2,2′‐Py 2 Se 2 ) have been determined. The reaction of Na 2 Se 2 with 2‐BrC 5 H 4 N (2‐BrPy) leads to a tautomeric mixture of pyridine‐2‐selenol (2‐PySeH) and pyridine‐2(1 H )‐selone (2‐PyHSe), which have been investigated by spectroscopic means. Additionally, the crystal structure of the latter has been determined. Reductive cleavage of the Se−Se bond in 2,2′‐Py 2 Se 2 with KB s Bu 3 H leads to K‐2‐SePy, which was trapped, either as [(18‐crown‐6)K] + [2‐PySe] − , whose structure contains polymeric cation−anion chains, or as [Et 4 N] + [2‐PySe] − . Reactions of K‐2‐SePy or [Et 4 N] + [2‐PySe] − with Ph 2 PCl, t Bu 2 PCl, or t BuPBr 2 lead to the corresponding, extremely air‐sensitive (pyridyl)selenophosphanes Ph 2 P‐2‐SePy, t Bu 2 P‐2‐SePy, and t BuP(2‐SePy) 2 . The latter was trapped as t BuP(O)(2‐SePy) 2 , whose crystal structure has been determined. Metal complexes of these (pyridyl)selenophosphanes have been prepared starting from the phosphane and CuBr, AgBr, (tht)AuCl (tht = tetrahydrothiophene), or [(η 6 ‐C 7 H 8 )Mo(CO) 3 ], in one‐pot syntheses. All crystal structures of the resulting metallacycles [({(C 5 H 4 N‐2‐Se) t Bu 2 P}‐ N , P )Cu(µ‐Br)] 2 , [({(C 5 H 4 N‐2‐Se) t Bu 2 P}‐ N , P )Ag(µ‐Br)] 2 , [({(C 5 H 4 N‐2‐Se) t Bu 2 P}‐ P )AuCl], and [({(C 5 H 4 N‐2‐Se) 2 t BuP}‐ N , N′ , P )Mo(CO) 3 ], were determined. Additionally, comprehensive spectroscopic investigations are presented.