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Metallochain Cluster Complexes and Metallomacrocyclic Triangles Based on Coordination Bonds between Palladium or Platinum and Diphosphinoacetylene Ligands
Author(s) -
Baumgartner Thomas,
Huynh Keith,
Schleidt Silvia,
Lough Alan J.,
Manners Ian
Publication year - 2002
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 - 10.1002/1521-3765(20021018)8:20<4622::aid-chem4622>3.0.co;2-v
Subject(s) - palladium , platinum , cluster (spacecraft) , chemistry , crystallography , computer science , catalysis , organic chemistry , operating system
To explore the potential of the coordination chemistry of Pd and Pt halides with phosphinoacetylene ligands for the generation of novel, highly metallated organometallic coordination polymers, investigations on model compounds [MX 2 (PPh 2 CCPh) 2 ] that exhibit trans ‐configured Pd centers and cis ‐configured Pt centers have been performed. The molecular structure of the trans‐ Pd complexes 2 (M=Pd, X=Br) and 5 (M=Pd, X=I) appeared suitable for the generation of linear materials, whereas the cis‐ Pt complex 6 (M=Pt, X=I) suggested the prospective formation of ring systems. The presence of acetylene moieties allowed for further increase of metal concentration by cluster formation with [Co 2 (CO) 8 ]. Two novel bimetal cluster complexes 7 and 8 were obtained from 5 and 6 , respectively, and these exhibit a bridging iodine ligand as an interesting structural motif leading to heterocyclic systems with M‐I‐Co‐C‐P skeletons (M=Pd or Pt). A similar approach with [Fe 2 (CO) 9 ] led to the formation of several products, including an unusual Pd–Fe cluster‐containing compound 10 . The extension of the coordination strategy to rigid bis(phosphinoacetylene) ligands gave rise to strained ring systems. Surprisingly, for the cis ‐configured PtCl 2 center, a rarely observed triangular structure 12 was obtained exclusively. The corresponding PtI 2 analog, 13 a rearranged over time to form a “ring‐fused” system 13 b with an extended BINAP‐like ligand.