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From a Phosphaketenyl‐Functionalized Germylene to 1,3‐Digerma‐2,4‐diphosphacyclobutadiene
Author(s) -
Yao Shenglai,
Xiong Yun,
Szilvási Tibor,
Grützmacher Hansjörg,
Driess Matthias
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201600701
Subject(s) - chemistry , germanium , yield (engineering) , ligand (biochemistry) , phosphorus , metathesis , medicinal chemistry , stereochemistry , crystallography , organic chemistry , materials science , polymerization , biochemistry , receptor , silicon , metallurgy , polymer
The first 4π‐electron resonance‐stabilized 1,3‐digerma‐2,4‐diphosphacyclobutadiene [L H 2 Ge 2 P 2 ] 4 (L H =CH[CHNDipp] 2 Dipp=2,6‐ i Pr 2 C 6 H 3 ) with four‐coordinate germanium supported by a β‐diketiminate ligand and two‐coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl‐functionalized N‐heterocyclic germylene [L H Ge‐P=C=O] 2 a prepared by salt‐metathesis reaction of sodium phosphaethynolate (P≡C−ONa) with the corresponding chlorogermylene [L H GeCl] 1 a . Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium–phosphorus triply bonded species [L H Ge≡P] 3 a , which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67 % yield. Notably, release of CO from the bulkier substituted [L tBu Ge‐P=C=O] 2 b (L tBu =CH[C( t Bu) N ‐Dipp] 2 ) furnishes, under concomitant extrusion of the diimine [Dipp‐NC( t Bu)] 2 , the bis‐N,P‐heterocyclic germylene [DippNC( t Bu)C(H)PGe] 2 5 .