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Synthesis and Coordination Ability of a Donor‐Stabilised Bis‐Phosphinidene
Author(s) -
Hadlington Terrance J.,
Kostenko Arseni,
Driess Matthias
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004300
Subject(s) - chemistry , ligand (biochemistry) , phosphinidene , chelation , cationic polymerization , denticity , lone pair , transition metal , metal , medicinal chemistry , stereochemistry , photochemistry , catalysis , polymer chemistry , inorganic chemistry , organic chemistry , molecule , biochemistry , receptor
Abstract Chelating phosphines have long been a mainstay as efficient directing ligands in transition‐metal catalysis. Low‐valent derivatives, namely chelating phosphinidenes, are to date unknown, and could lead to chelating complexes containing more than one metal centre due to the intrisic capacity of phosphinidenes to bind two metal fragments at one P‐centre. Here we describe the synthesis of the first such chelating bis‐phosphinidene ligand, XantP 2 ( 2 ), generated by the reduction of a diphosphino xanthene derivative, Xant(PH 2 ) 2 ( 1 ) with i Pr NHC ( i Pr NHC=[:C{N( i Pr)C(H)} 2 ]). Initial studies have shown that this novel chelating ligand can act as a bidentate ligand towards element dihalides (i.e. FeCl 2 , ZnI 2 , GeCl 2 , SnBr 2 ), forming cationic complexes with the tetryl elements. In contrast, XantP 2 demonstrates an ability to bind multiple metal centres in the reaction with CuCl, leading to a cationic Cu 3 P 3 ring complex, with Cu centres bridged by phosphinidene arms. Density Functional Theory calculations show that 2 indeed holds 4 lone pairs of electrons, shedding further light on the coordination capacity for this novel ligand class through observation of directionality and hybridisation of these electron pairs.