In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2006, No. 1 ( 2006-01), p. 115-126
Abstract:
The reaction of [Cu(NCMe) 4 ]PF 6 with piperidinium 2,7‐di‐ tert ‐butyl‐9 H ‐fluorene‐9‐carbodithioate (pipH)[S 2 C( t Bu‐Hfy)] ( 1 ; t Bu‐Hfy = 2,7‐di‐ tert ‐butylfluoren‐9‐yl), affords [Cu n {S 2 C( t Bu‐Hfy)} n ] ( 2 ), which reacts with various P ligands to give [Cu{S 2 C( t Bu‐Hfy)}L 2 ] [L = PPh 3 ( 3a ), PCy 3 ( 3b ), P i Pr 3 ( 3d ); L 2 = 1,1′‐bis(diphenylphosphanyl)ferrocene (dppf, 3c ), bis(diphenylphosphanyl)methane (dppm, 3e )]. Compounds 3a – c react with atmospheric oxygen and moisture in the presence of NEt 3 to give the dinuclear complexes [Cu 2 {[SC=( t Bu‐fy)] 2 S}L 2 ] [ t Bu‐fy = 2,7‐di‐ tert ‐butylfluoren‐9‐ylidene; L = PPh 3 ( 4a ), PCy 3 ( 4b ); L 2 = dppf ( 4c )], which contain a new dithiolato ligand formally resulting from the condensation of two dithioato ligands with loss of a sulfide ion and two protons. Neutral Cu I dithiolate complexes of the type [Cu 4 {S 2 C=( t Bu‐fy)} 2 L 4 ] [S 2 C=( t Bu‐fy) = [2,7‐di‐ tert ‐butylfluoren‐9‐ylidene)methanedithiolate; L = PPh 3 ( 5a ), P(C 6 H 4 OMe‐ p ) 3 ( 5b ), P i Pr 3 ( 5d ) or L 2 = dppf ( 5c )] were obtained by treating 1 with [Cu(NCMe) 4 ]PF 6 , the corresponding phosphane, and piperidine in a 1:2:2:1 molar ratio. The reaction of 1 with Cu(ClO 4 ) 2 · 6H 2 O and (Pr 4 N)OH in a 2:1:2 molar ratio gives the Cu II complex (Pr 4 N) 2 [Cu{S 2 C=( t Bu‐fy)} 2 ] [(Pr 4 N) 2 6 ], which readily oxidizes to the Cu III complex Pr 4 N[Cu{S 2 C=( t Bu‐fy)} 2 ] (Pr 4 N 7 ) in the presence of atmospheric oxygen and moisture. The salt PPN 7 [PPN + =(Ph 3 P) 2 N + ] was obtained from 1 , CuCl 2 · 2H 2 O, PPNCl, and piperidine in a 2:1:1:2 molar ratio under aerobic conditions. The crystal structures of 3a , 3c· CH 2 Cl 2 , 4a· 4Me 2 CO, and 4c· CH 2 Cl 2 have been determined by X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2006:1
DOI:
10.1002/ejic.200500613
Language:
English
Publisher:
Wiley
Publication Date:
2006
detail.hit.zdb_id:
1475009-0
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