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Rhodium(III)‐Assisted Nucleophilic Addition of Ammonia to Metal‐Bound Benzyl Cyanide: Crystal Structures of mer ‐[RhCl 3 (PhCH 2 CN) 3 ]·1/2 C 6 H 5 CH 3 and mer ‐[RhCl 3 {PhCH 2 C(NH 2 )=NH} 3 ]
Author(s) -
Kukushkin Vadim Yu.,
Ilichev Igor V.,
Wagner Gabriele,
Revenco Mikhail D.,
Kravtsov Viktor H.,
Suwinska Kinga
Publication year - 2000
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/(sici)1099-0682(200006)2000:6<1315::aid-ejic1315>3.0.co;2-8
Subject(s) - chemistry , rhodium , toluene , medicinal chemistry , cyanide , nitrile , crystal structure , inorganic chemistry , amidine , coordination sphere , organic chemistry , polymer chemistry , catalysis
Heating of [RhCl 3 (MeCN) 3 ] in benzyl cyanide at 100 °C gives the substitution product mer ‐[RhCl 3 (PhCH 2 CN) 3 ] (90% yield), whose recrystallization from an acetone/toluene mixture leads to formation of the toluene solvate mer ‐[RhCl 3 (PhCH 2 CN) 3 ]·1/2 C 6 H 5 Me. The crystal structure of the latter, determined by X‐ray single‐crystal diffractometry, shows an unusual self‐assembly due to intermolecular CH ··· Cl hydrogen bonding with concomitant clathration of toluene. Diffusion of ammonia into a solution of mer ‐[RhCl 3 (PhCH 2 CN) 3 ] in neat benzyl cyanide brings about a facile rhodium(III)‐assisted addition of NH 3 to the coordinated nitrile species to produce the amidine complex mer ‐[RhCl 3 {PhCH 2 C(NH 2 )=NH} 3 ] (83% yield). Both starting material and the product were characterized by elemental analyses, FAB‐MS, IR and 1 H and 13 C{ 1 H} NMR spectroscopy. The crystal structure of mer ‐[RhCl 3 {PhCH 2 C(NH 2 )=NH} 3 ] provides the first example of a rhodium(III) complex with a monodentate amidine ligand.