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Cyclooligomerization Reactions of Different Phosphaalkynes in the Presence of [W(CO) 5 thf] − A Route to Tungsten‐Stabilised Phosphorus Heterocycles
Author(s) -
Kramkowski Peter,
Scheer Manfred
Publication year - 2000
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(200008)2000:8<1869::aid-ejic1869>3.0.co;2-a
Subject(s) - chemistry , yield (engineering) , ligand (biochemistry) , reactivity (psychology) , moiety , coordination sphere , tungsten , medicinal chemistry , stereochemistry , crystallography , organic chemistry , crystal structure , receptor , metallurgy , medicine , biochemistry , materials science , alternative medicine , pathology
The reactivity of various phosphaalkynes versus [W(CO) 5 thf] has been studied. The reaction with Mes*C≡P (Mes* = 2,4,6‐ t Bu 3 C 6 H 2 ) exclusively leads to the low yield formation of [W(CO) 2 {(η 2 ‐PCMes*)W(CO) 5 } 2 ] ( 1 ). The reaction of the less bulky tBuC≡P with [W(CO) 5 thf] results in high yields in [W(CO) 2 {η 4 ‐( t BuC) 2 P 2 W(CO) 5 }{η 2 ‐(tBuCP)W(CO) 5 }] ( 2 ) which possesses a 1,3‐diphosphete ligand as well as a side‐on coordinated tBuCP unit. Experiments employing MesC≡P (Mes = 2,4,6‐Me 3 C 6 H 2 ) give the complexes [W(CO) 4 {η 4 ‐(MesC) 2 P 2 }] ( 3 ), [W(CO) 2 {η 4 ‐(MesC) 2 P 2 }{η 2 ‐(MesCP)W(CO) 5 }] ( 4 ) and [W(CO) 2 {η 4 ‐(MesC) 2 P 2 W(CO) 5 }〈η 2 ‐(MesCP)W(CO) 5 {µ‐W(CO) 4 }〉] ( 5 ) which have a 1,3‐diphosphete ligand in their coordination sphere and are partly substituted with an additional side‐on coordinated MesC≡P unit. In 5 , two P atoms of the 1,3‐diphosphete and the side‐on coordinated MesC≡P are further bridged by a W(CO) 4 moiety. Additionally, the unusual product [{W(CO) 3 }〈η 6 ‐1,2,4‐(RC) 3 P 3 {RCP→W(CO) 5 } 2 〉] (R = Mes) ( 6 ) resulting from a pentamerization of MesC≡P initiated by [W(CO) 5 thf], could be obtained in moderate yield. Comprehensive spectroscopical and structural investigations of all products are presented.