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Phosphanylphosphinidene‐Phosphoranes: A Study on Building and Decomposition of Phosphorus‐Rich Chains with Two Ylidic Moieties
Author(s) -
Matern Eberhard,
Anson Christopher E.,
Baum Elke,
Sattler Ewald,
Kovács Ilona
Publication year - 2020
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/ejic.202000073
Subject(s) - chemistry , thermal decomposition , substituent , ring (chemistry) , stereochemistry , trimer , derivative (finance) , crystal structure , decomposition , medicinal chemistry , crystallography , dimer , organic chemistry , financial economics , economics
The reactions of t Bu 2 P–P=P( t Bu 2 )CH 2 Li at low temperature with dichlorophosphanes RPCl 2 (R = Ph, Me, NEt 2 , t Bu) lead to “P‐7‐chains” as primary products wherein two ylidic moieties are linked by a CH 2 –PR–CH 2 unit. However, if R = t Bu the long chain is only a by‐product in addition to t Bu 2 P–P=P( t Bu 2 )Me. The thermal decomposition of “P‐7‐chains” as monitored by 31 P NMR spectroscopy results in t Bu 2 P–CH 2 –PR–CH 2 –P t Bu 2 (“P‐3‐chains”) and the phosphanylphosphanylidene { t Bu 2 P–P} which is observed as its cyclic trimer or tetramer. In the reactions of t Bu(Me 3 Si)P–P=P( t Bu 2 )CH 2 Li with RPCl 2 the corresponding “P‐7‐chains” and the P 4 CH 2 ‐rings are formed. The substituent R strongly determines the ratio of chain to ring as well as the thermal stability of the products. The solid‐state structures of one representative of both “P‐7‐chains”, and of the oxidized derivative of the P 4 CH 2 ‐ring with R = t Bu were determined by single‐crystal X‐ray diffraction analysis.