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Reactivity of Dinuclear Copper(I)/pybox Complexes towards Isocyanides and Phosphanes
Author(s) -
Panera María,
Díez Josefina,
Merino Isabel,
Rubio Eduardo,
Gamasa M. Pilar
Publication year - 2011
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.201000974
Subject(s) - chemistry , denticity , pyridine , isocyanide , reactivity (psychology) , stereochemistry , copper , medicinal chemistry , ligand (biochemistry) , metal , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
The dinuclear complexes [Cu 2 (R‐pybox) 2 ][PF 6 ] 2 {R‐pybox = 2,6‐bis[4′‐( S )‐isopropyloxazolin‐2′‐yl]pyridine for ( S , S )‐ i Pr‐pybox ( 1 ) and 2,6‐bis[4′‐( R )‐phenyloxazolin‐2′‐yl]pyridine for ( R , R )‐Ph‐pybox ( 2 )} are very efficient precursors for the synthesis of dinuclear and mononuclear derivatives containing isocyanide or phosphane ligands. The reaction of 1 and 2 with the isocyanides (CNBn or CNCy) resulted in the synthesis of the dinuclear derivatives [Cu 2 (R‐pybox) 2 (CNBn) 2 ][PF 6 ] 2 [R‐pybox = ( S , S )‐ i Pr‐pybox ( 3 ), ( R , R )‐Ph‐pybox ( 4 )] and [Cu 2 (R‐pybox) 2 (CNCy) 2 ][PF 6 ] 2 [R‐pybox = ( S , S )‐ i Pr‐pybox ( 5 ), ( R , R )‐Ph‐pybox ( 6 )]. When the reaction was carried out with the monodentate (PMePh 2 , PPh 3 ) and the bidentate phosphanes [dppm, dppf, ( S )‐peap] the mononuclear complexes [Cu(R‐pybox)(PRPh 2 ) 2 ][PF 6 ] [R‐pybox = ( S , S )‐ i Pr‐pybox, R = Me( 7 ), Ph ( 8 ); R‐pybox = ( R , R )‐Ph‐pybox, R = Ph ( 9 )], [Cu(R‐pybox){( S )‐peap}][PF 6 ] [R‐pybox = ( S , S )‐ i Pr‐pybox ( 11 ), ( R , R )‐Ph‐pybox ( 12 )], and [Cu(R‐pybox)(dppf)][PF 6 ] [R‐pybox = ( S , S )‐ i Pr‐pybox ( 13 ), ( R , R )‐Ph‐pybox ( 14 )] and the dinuclear complex [Cu 2 {( S , S )‐ i Pr‐pybox}(μ‐dppm) 2 ][PF 6 ] 2 ( 10 ) were obtained, respectively. The structures of complexes 3 , 7 , 10 , and 13 have been resolved by X‐ray diffraction methods and by 1D, 2D, and DOSY NMR spectroscopy measurements. The 1 H, 31 P, and 19 F DOSY NMR spectroscopic experiments provided evidence that the solid‐state nuclearity of compounds 3 , 7 , 10 , and 13 is maintained in solution and confirmed that these ionic compounds exist in solution as stable, discrete, cationic complexes.