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Coordination chemistry of H‐spirophosphorane ligands towards pentacarbonylchlororhenium(I) – synthesis, structure and catalytic activity of complexes
Author(s) -
Skarżyńska Anna,
Siczek Miłosz,
Gawryszewska Paula,
Chaczko Karolina
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5756
Subject(s) - chemistry , rhenium , denticity , catalysis , medicinal chemistry , coordination complex , ligand (biochemistry) , stereochemistry , crystal structure , crystallography , inorganic chemistry , organic chemistry , metal , biochemistry , receptor
Synthesis of a group of carbonyl rhenium coordination compounds with hydrospirophosphorane ligands was carried out and described. Different symmetrical HP(OCH 2 CH 2 NH) 2 L1 , HP(OCH 2 CMe 2 NH) 2 L2 , HP(OC 6 H 4 NH) 2 L3 , and unsymmetrical ligands HP (OCMe 2 CMe 2 O)(OC 6 H 4 NH) L4 were found to coordinate to the rhenium center as bidentate P,N donor ligands yielding fac ‐[ReCl (CO) 3 Ln ], where n = 1 – 4. Furthermore, monodentate coordination was also observed in some cases, as was clearly presented in the case of [ReCl(CO) 2 ( L4‐ κ 2 P , N )( L4‐ κ P )] complex. All of the complexes were characterized using optical spectroscopy. Single‐crystalX‐ray diffraction was also performed in the case of fac ‐[ReCl(CO) 3 L3 ], fac ‐[ReCl(CO) 3 L4 ], [Re(CO) 2 ( L2 ) 2 ]Cl and [ReCl (CO) 2 ( L4‐ κ 2 P , N )( L4‐ κ P )] samples. Complexes [ReCl(CO) 3 L3 ] and [ReCl (CO) 3 L4 ], both bearing rings of conjugated double bonds within hydrospirophosphorane ligands, exhibited luminescence. Catalytic properties of rhenium complexes were assessed using the representative fac ‐[ReCl (CO) 3 L2 ] complex in the dimerization reaction of terminal alkynes. An efficient and selective procedure for synthesis of the E ‐ enynes was developed. Coupling of (2‐chlorophenyl)acetylene was mediated by [ReCl (CO) 3 L2 ]/TBAF system with a 100% conversion rate. Different substituents within aromatic alkynes were tolerated and the resulting products were dependent on the nature of the substituents.