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Synthesis and Structures of Rh I and Ir I Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts
Author(s) -
Doddi Adinarayana,
Bockfeld Dirk,
Tamm Matthias
Publication year - 2019
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201800440
Subject(s) - rhodium , chemistry , phosphinidene , adduct , carbene , medicinal chemistry , iridium , carbon monoxide , infrared spectroscopy , trimethylsilyl , catalysis , organic chemistry
N‐Heterocyclic carbene‐phosphinidene adducts of the type (IDipp)PR [R = Ph ( 5 ), SiMe 3 ( 6 ); IDipp = 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] were used as ligands for the preparation of rhodium(I) and iridium(I) complexes. Treatment of (IDipp)PPh ( 5 ) with the dimeric complexes [M(μ‐Cl)(COD)] 2 (M = Rh, Ir; COD = 1,5‐cyclcooctadiene) afforded the corresponding metal(I) complexes [M(COD)Cl{(IDipp)PPh}] [M = Rh ( 7 ) or Ir ( 8 )] in moderate to good yields. The reaction of (IDipp)PSiMe 3 ( 6 ) with [Ir(μ‐Cl)(COD)] 2 did not yield trimethylsilyl chloride elimination product, but furnished the 1:1 complex, [Ir(COD)Cl{(IDipp)PSiMe 3 }] ( 9 ). Additionally, the rhodium‐COD complex 7 was converted into the corresponding rhodium‐carbonyl complex [Rh(CO) 2 Cl{(IDipp)PPh}] ( 10 ) by reaction with an excess of carbon monoxide gas. All complexes were fully characterized by NMR spectroscopy, microanalyses, and single‐crystal X‐ray diffraction studies.