Premium
Synthesis and Characterization of Linear Tetranuclear Silver(I) Complexes Bridged by Tetraphosphane Ligands
Author(s) -
Takemura Yukie,
Nakajima Takayuki,
Tanase Tomoaki
Publication year - 2009
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.200900652
Subject(s) - chemistry , isocyanide , stereochemistry , medicinal chemistry , crystallography
Reactions of AgOTf with meso ‐bis[(diphenylphosphanylmethyl)phenylphosphanyl]methane (dpmppm) afforded[Ag 4 (OTf) 2 (μ‐OTf)(μ‐dpmppm) 2 {(CH 3 ) 2 CO}](OTf) ( 1 ) and [Ag 4 (OTf) 2 (μ‐OTf)(μ‐dpmppm) 2 (RNC) 2 ](OTf) {R = Xyl ( 2a ), Mes ( 2b ), t Bu ( 2c )}. When AgOTf was treated with dpmppm in air in the presence of t BuNC, cleavage of the C–Cl and P–C bonds occurred to give [Ag 4 (μ‐Cl)(μ‐dpmppm) 2 ( t BuNC) 4 ](OTf) 3 ( 3 ) and [Ag 4 (μ‐Ph 2 PO 2 )(μ‐dpmppm) 2 ( t BuNC) 3 ](OTf) 3 ( 4 ). Reaction of AgOCOCF 3 with dpmppm resulted in [Ag 4 (OCOCF 3 ) 2 (μ‐OCOCF 3 )(μ‐dpmppm) 2 ](CF 3 COO) ( 5 ). By treatment of AgPF 6 with dpmppm, [Ag 4 (μ‐dpmppm) 2 ( t BuNC) 4 ](PF 6 ) 4 ( 6 ) and [Ag 4 (PO 2 F 2 ) 2 (μ‐dpmppm) 2 ( t BuNC) 2 ] (PF 6 ) 2 ( 7 ) were obtained. Wheareas complexes 1 – 3 possess a {Ag 4 (μ‐dpmppm) 2 } 4+ core in which the Ag 4 strings are rather bent with two dpmppm ligands arranged in a syn fashion, complexes 4 – 7 have linear Ag 4 strings supported by two dpmppm ligands arranged in an anti fashion. These results suggest that the dpmppm‐supported tetrasilver(I) strings are quite flexible and labile and thus are potentially important in promoting organic reactions as a result of the multimetallic centers.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)